CN110330530A - Iridium metal complex and preparation method thereof and organic electroluminescence device containing the compound - Google Patents
Iridium metal complex and preparation method thereof and organic electroluminescence device containing the compound Download PDFInfo
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- CN110330530A CN110330530A CN201910619237.0A CN201910619237A CN110330530A CN 110330530 A CN110330530 A CN 110330530A CN 201910619237 A CN201910619237 A CN 201910619237A CN 110330530 A CN110330530 A CN 110330530A
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- -1 Iridium metal complex Chemical class 0.000 title claims abstract description 44
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 35
- 238000005401 electroluminescence Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 150000001875 compounds Chemical class 0.000 title abstract description 27
- 125000001424 substituent group Chemical group 0.000 claims abstract description 27
- 239000003446 ligand Substances 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims abstract description 11
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 11
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 11
- 150000002367 halogens Chemical class 0.000 claims abstract description 11
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 9
- 238000006467 substitution reaction Methods 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 claims 1
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 3
- 150000002902 organometallic compounds Chemical class 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229960000935 dehydrated alcohol Drugs 0.000 description 6
- 239000002019 doping agent Substances 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 101100490479 Lactococcus lactis subsp. lactis (strain IL1403) addA gene Proteins 0.000 description 2
- 101100000975 Lactococcus lactis subsp. lactis (strain IL1403) rexB gene Proteins 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
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
-
- 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
-
- 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
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention relates to a kind of iridium metal complex and preparation method thereof and containing the organic electroluminescence device of the compound, the iridium metal complex its structural formula as described in chemical formula 1:Wherein: R1、R2、R3And R4It is each independently selected from the condensed ring radical of hydrogen, deuterium, halogen, cyano, substituted or non-substituted C1-C6 alkyl, substituted or non-substituted C6-C18 aryl, substituted or non-substituted C4-C12 aromatic heterocyclic radical or substituted or non-substituted C8~C16；R1、R2、R3The position of substitution is any position of place ring；R1、R2The quantity of substituent group is 0~2, R3The quantity of substituent group is 0~4.New structural iridium metal complex provided by the invention, by selecting the ligand binding of specific heterocycle, the wavelength of modulating compound, obtained organo-metallic compound is after for organic electroluminescence device, so that the luminous efficiency of device and brightness improve.The preparation method of iridium metal complex provided by the invention, preparation step is simple, and product purity is high.
Description
Technical field
The present invention relates to organic photoelectrical material fields, and in particular to a kind of iridium metal complex and preparation method thereof and contains
The organic electroluminescence device of the compound.
Background technique
Organic electroluminescent technology is latest generation flat panel display, can be used for flat-panel monitor and lighting source, mesh
The flat-panel monitor of preceding commercialization has put goods on the market.Lighting source is since the absolute predominance of its own is also quickly by industrialization.Electricity
Electroluminescence device has structure of whole solid state, and electroluminescent organic material is core and the basis for constituting the device.New material is opened
Hair is the driving source for pushing electroluminescent technology to be constantly progressive.It is also present organic electroluminescence to the preparation of original material and device optimization
The research hotspot for the industry of shining.
And phosphorescence luminescence phenomenon is since discovery, is constantly subjected to that everybody chase after is high, because of the luminous efficiency of phosphor material
It is apparently higher than fluorescence radiation efficiency, can theoretically reach 100% luminous efficiency, so many scientific research institutions are all increasing phosphorus
The R&D intensity of material, it is intended to which industrialized development is accelerated by phosphor material.But since phosphor material synthesis price compares
Height, synthesis technology requirement is relatively high, and is easy pollution environment in the synthesis process, and purification requires relatively high, low efficiency.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
The invention solves in the prior art the technical issues of, a kind of iridium metal complex and preparation method thereof is provided and is contained
There is the organic electroluminescence device of the compound.New structural iridium metal complex provided by the invention, it is specific by selecting
Heterocycle ligand binding, the wavelength of modulating compound, obtained organo-metallic compound be used for organic electroluminescence device
Afterwards, so that the luminous efficiency of device and brightness improve.
In order to solve the above-mentioned technical problem, technical solution of the present invention is specific as follows:
The present invention provides a kind of iridium metal complex, structural formula as described in chemical formula 1:
Chemical formula 1
Wherein: R1、R2、R3And R4It is each independently selected from hydrogen, deuterium, halogen, cyano, substituted or non-substituted C1-C6 alkane
Base, substituted or non-substituted C6-C18 aryl, substituted or non-substituted C4-C12 aromatic heterocyclic radical or substituted or non-substituted C8
The condensed ring radical of~C16；
R1、R2、R3The position of substitution is any position of place ring；R1、R2The quantity of substituent group is 0~2, R3Substituent group
Quantity is 0~4.
In the above-mentioned technical solutions, the alkyl is straight chained alkyl, branched alkyl, naphthenic base, the substitution of at least one substituent group
Direct-connected alkyl, at least one substituent group replace branched alkyl or at least one substituent group replace naphthenic base；Wherein, described to take
It is independent selected from one or more of halogen, deuterium, cyano, hydroxyl and sulfydryl for base.
In the above-mentioned technical solutions, the aryl is preferably the aryl that unsubstituted aryl or at least one substituent group replace；
Wherein, the substituent group is independent is selected from halogen, deuterium, amino, cyano, nitro, hydroxyl or sulfydryl.
In the above-mentioned technical solutions, the aromatic heterocyclic radical is preferably that unsubstituted heteroaryl or at least one substituent group take
The aromatic heterocyclic radical in generation；Wherein, the hetero atom in heteroaryl is nitrogen, sulphur or oxygen；The substituent group it is independent selected from halogen, deuterium,
Amino, cyano, nitro, hydroxyl or sulfydryl.
In the above-mentioned technical solutions, R1、R2、R3It is independent with place ring on other substituent groups mutually form substitution or
Non-substituted C3~C30 aliphatic ring, substituted or non-substituted C6~C60 aromatic ring, substituted or non-substituted C2~C60 virtue are miscellaneous
Ring, substituted or non-substituted C6~C60 condensed ring or substituted or non-substituted C5~C60 loop coil；
Or R1、R2、R3Between mutually form substituted or non-substituted C3~C30 aliphatic ring, substituted or non-substituted C6
~C60 aromatic ring, substituted or non-substituted C2~C60 heteroaromatic, substituted or non-substituted C6~C60 condensed ring replace or non-take
C5~C60 loop coil in generation；
Substituent group on the aforementioned substituent group is at least selected from hydrogen, deuterium, halogen, cyano, substituted or non-substituted C1-C6
Alkyl, substituted or non-substituted C6-C18 aryl, substituted or non-substituted C4-C12 aromatic heterocyclic radical, substituted or non-substituted C8
One of the condensed ring radical of~C16, substituted or non-substituted C5~C60 loop coil.
In the above-mentioned technical solutions, the iridium metal complex is selected from any one in flowering structure:
In the above-mentioned technical solutions, the most preferably described iridium metal complex is selected from any one in flowering structure:
Some specific structure types are only listed above, but this series compound does not limit to above-mentioned molecular structure, it is all
It is that the simple transformation of these groups and its these substituted groups and the position of substitution can be obtained by other specific molecular structures,
This is no longer going to repeat them.
The present invention also provides a kind of preparation methods of iridium metal complex, comprising the following steps:
Step 1 sufficiently reacts raw material A with iridous chloride, and bridge ligand intermediate B is made；
Step 2 sufficiently reacts intermediate B with intermediate C, and iridium metal complex described in chemical formula 1 is made；
Its synthetic route is as follows:
Wherein, R1、R2、R3、R4And its range limited in respective substituent group quantity and chemical formula 1 is consistent, here not
It repeats again.
The present invention also provides a kind of organic electroluminescences comprising iridium metal complex shown in chemical formula 1 of the present invention
Part.
The organic electroluminescence device includes:
First electrode, second electrode and the organic matter layer being placed between two electrode, wherein wrapped in the organic matter layer
Contain iridium metal complex shown in chemical formula 1 of the present invention；Iridium metal complex shown in chemical formula 1 of the present invention can be single
Form is mixed in organic matter layer with other materials.
The organic matter layer includes at least hole injection layer, hole transmission layer, had both had hole injection but also with hole biography
Defeated technical ability layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer and not only have electron-transport but also
Has one or more of electron injection technical ability layer.
The organic electroluminescence device, which contains iridium metals shown in chemical formula 1 of the present invention including at least one layer of functional layer, matches
Close object.
The organic electroluminescence device, including luminescent layer, the luminescent layer contain iraurite shown in chemical formula 1 of the present invention
Metal complex.It is preferred that the luminescent layer of the organic electroluminescence device includes material of main part and dopant material, the dopant material
For iridium metal complex shown in chemical formula 1 of the present invention.The mixing ratio of further preferred luminescent layer material of main part and dopant material
Example is 90:10~99.5:0.5.
Device of the present invention can be used for organic luminescent device, organic photovoltaic cell, Electronic Paper, Organophotoreceptor or
Organic Thin Film Transistors.
The beneficial effects of the present invention are:
New structural iridium metal complex provided by the invention is adjusted by selecting the ligand binding of specific heterocycle
The wavelength of compound, obtained organo-metallic compound is after for organic electroluminescence device, so that the luminous efficiency of device
And brightness improves.
The preparation method of iridium metal complex provided by the invention, preparation step is simple, and product purity is high.
Specific embodiment
In order to which method of the invention is further described, it is exemplified below more detailed embodiment and is illustrated.
1 prepare compound L001 of embodiment
Step 1, under nitrogen protection system, weigh A-001 (83.0mmol, 20g), IrCl3·3H2O28.4mmo1 is (i.e.
It 10g) is put into reaction system, the mixed solution of 600mL ethylene glycol ethyl ether and 200mL pure water is added, flows back under nitrogen protection
It 24 hours, is then cooled to room temperature, there is Precipitation, precipitating is filtered, successively rinses drying with water, dehydrated alcohol, petroleum ether,
Obtain the bridge ligand B-001 (12g, yield 60%) of red powder.
Step 2 weighs -001 8.6mmol of intermediate B (i.e. 12g), and ligand 3,7- diethyl -4,6- nonyl diketone C- is added
001 (5.5g), then add ethylene glycol ethyl ether 250mL and potassium carbonate (12g) into system, under nitrogen protection, 120 DEG C of stirrings 24 are small
When, it filters, alcohol is washed, and is dried, is made solvent with methylene chloride, and with silica gel column chromatography, filtrate thickened solid is precipitated, and obtains final red
Compound L 001 (7g, yield 46.7%).
HPLC purity: greater than 99%.
Mass spectrum: calculated value 872.19；Test value is 872.15.
Elemental analysis: calculated value C:64.72%；H:6.36%；N:3.21%；O:3.67%；Ir:22.04%；Test value
Are as follows: C:64.71%；H:6.35%；N:3.22%；O:3.66%；Ir:22.05%.
2 prepare compound L012 of embodiment
Step 1, under nitrogen protection system, weigh A-012 (83.0mmol, 20g), IrCl3·3H2O28.4mmo1 is (i.e.
It 10g) is put into reaction system, the mixed solution of 600mL ethylene glycol ethyl ether and 200mL pure water is added, flows back under nitrogen protection
It 24 hours, is then cooled to room temperature, there is Precipitation, precipitating is filtered, successively rinses drying with water, dehydrated alcohol, petroleum ether,
Obtain the bridge ligand B-012 (12g, yield 60%) of red powder.
Step 2 weighs -012 8.6mmol of intermediate B (i.e. 12g), is added ligand C-012 (4g), then adds second into system
Glycol ether 240mL and potassium carbonate (12g), under nitrogen protection, 120 DEG C are stirred 24 hours, are filtered, and alcohol is washed, and are dried, are used dichloromethane
Alkane makees solvent, and with silica gel column chromatography, filtrate thickened solid is precipitated, and obtains the compound L 001 (7g, yield 50%) of final red.
HPLC purity: greater than 99%.
Mass spectrum: calculated value 816.08；Test value is 816.05.
Elemental analysis: calculated value C:63.29%；H:5.81%；N:3.21%；O:3.92%；Ir:23.55%；Test value
Are as follows: C:63.30%；H:5.82%；N:3.22%；O:3.90%；Ir:23.56%.
3 prepare compound L025 of embodiment
Step 1, under nitrogen protection system, weigh A-025 (83.0mmol, 20g), IrCl3·3H2O28.4mmo1 is (i.e.
It 10g) is put into reaction system, the mixed solution of 600mL ethylene glycol ethyl ether and 200mL pure water is added, flows back under nitrogen protection
It 24 hours, is then cooled to room temperature, there is Precipitation, precipitating is filtered, successively rinses drying with water, dehydrated alcohol, petroleum ether,
Obtain the bridge ligand B-025 (12g, yield 60%) of red powder.
Step 2 weighs -025 8.6mmol of intermediate B (i.e. 12g), and ligand acetylacetone,2,4-pentanedione C-025 25.8mmol is added
(2.6g), then add ethylene glycol ethyl ether 250mL and potassium carbonate (12g) into system, under nitrogen protection, 120 DEG C are stirred 24 hours, are taken out
Filter, alcohol are washed, and petroleum ether is washed, and drying makees solvent with methylene chloride, and with silica gel column chromatography, filtrate thickened solid is precipitated, and are obtained final
Red compound L 025 (6g, yield 46.15%).
HPLC purity: greater than 99%.
Mass spectrum: calculated value 759.97；Test value is 756.00.
Elemental analysis: calculated value C:61.64%；H:5.17%；N:3.69%；O:4.21%；Ir:25.29%；Test value
For C:61.63%；H:5.18%；N:3.68%；O:4.20%；Ir:25.28%.
4 prepare compound L039 of embodiment
Step 1, under nitrogen protection system, weigh A-039 (76.0mmol, 20g), IrCl3·3H2O25.3mmo1 is (i.e.
It 8.9g) is put into reaction system, the mixed solution of 600mL ethylene glycol ethyl ether and 200mL pure water is added, flows back under nitrogen protection
It 24 hours, is then cooled to room temperature, there is Precipitation, precipitating is filtered, successively rinses drying with water, dehydrated alcohol, petroleum ether,
Obtain the bridge ligand B-039 (9g, yield 47.4%) of red powder.
Step 2 weighs -039 6mmol of intermediate B (i.e. 9g), is added ligand C-039 18mmol (3.8g), then to system
In plus ethylene glycol ethyl ether 180mL and potassium carbonate (8g), under nitrogen protection, 120 DEG C are stirred 24 hours, are filtered, and alcohol is washed, petroleum ether
It washes, dries, make solvent with methylene chloride, with silica gel column chromatography, filtrate thickened solid is precipitated, and obtains the compound of final red
L039 (5g, yield 45%).
HPLC purity: greater than 99%.
Mass spectrum: calculated value 928.29；Test value is 928.30.
Elemental analysis: calculated value C:65.99%；H:6.84%；N:3.02%；O:3.45%；Ir:20.71%；Test value
For C:66.0%；H:6.82%；N:3.04%；O:3.46%；Ir:20.70%.
5 prepare compound L059 of embodiment
Step 1, under nitrogen protection system, weigh A-059 (65.6mmol, 20g), IrCl3·3H2O21.9mmo1 is (i.e.
It 7.7g) is put into reaction system, the mixed solution of 600mL ethylene glycol ethyl ether and 200mL pure water is added, flows back under nitrogen protection
It 24 hours, is then cooled to room temperature, there is Precipitation, precipitating is filtered, successively rinses drying with water, dehydrated alcohol, petroleum ether,
Obtain the bridge ligand B-059 (9.15g, yield 50%) of red powder.
Step 2 weighs -059 5.5mmol of intermediate B (i.e. 9.15g), is added ligand C-05916.8mmol (3.1g), then
Into system plus ethylene glycol ethyl ether 250mL and potassium carbonate (8g), under nitrogen protection, 120 DEG C are stirred 24 hours, are filtered, and alcohol is washed, and are dried
It is dry, solvent is made with methylene chloride, with silica gel column chromatography, filtrate thickened solid is precipitated, and obtains the compound L 059 of final red
(4.3g, yield 40%).
HPLC purity is greater than 99%.
Mass spectrum: calculated value 984.40；Test value is 984.50.
Elemental analysis: calculated value C:67.11%；H:7.27%；N:2.85%；O:3.25%；Ir:19.53%；Test value
For C:67.12%；H:7.28%；N:2.86%；O:3.24%；Ir:19.52%.
6 prepare compound L065 of embodiment
Step 1, under nitrogen protection system, weigh A-065 (65.5mmol, 20g), IrCl3·3H2O21.8mmo1 is (i.e.
It 7.7g) is put into reaction system, the mixed solution of 600mL ethylene glycol ethyl ether and 200mL pure water is added, flows back under nitrogen protection
It 24 hours, is then cooled to room temperature, there is Precipitation, precipitating is filtered, successively rinses drying with water, dehydrated alcohol, petroleum ether,
Obtain the bridge ligand B-065 (9g, yield 49.4%) of red powder.
Step 2 weighs -065 5.4mmol of intermediate B (i.e. 9g), is added ligand C-065 16.2mmol (3g), then to body
In system plus ethylene glycol ethyl ether 180mL and potassium carbonate (7.5g), under nitrogen protection, 120 DEG C are stirred 24 hours, are filtered, and alcohol is washed, and are dried
It is dry, solvent is made with methylene chloride, with silica gel column chromatography, filtrate thickened solid is precipitated, and obtains the compound L 065 of final red
(5.1g, yield 48.4%).
HPLC purity is greater than 99%.
Mass spectrum: calculated value 984.40；Test value is 984.50.
Elemental analysis: calculated value C:67.11%；H:7.27%；N:2.85%；O:3.25%；Ir:19.53%；Test value
For C:67.12%；H:7.28%；N:2.86%；O:3.24%；Ir:19.52%.
The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device is by the iridium metals
Complex is made, and is more specifically made of the iridium metal complex shown in chemical formula 1.
In order to which the present invention is described in further detail, it is exemplified below more specific embodiment.
Embodiment 7
The compound L 001 prepared using embodiment 1 prepares organic electroluminescence device, more specifically:
It is by coating layer thicknessIto glass substrate be placed in distilled water and clean 2 times, ultrasonic washing 30 minutes,
It is cleaned repeatedly with distilled water 2 times, ultrasonic washing 10 minutes, after distilled water cleans, isopropanol, acetone, methanol equal solvent
It is dry after ultrasonic washing in order, it is transferred in plasma washing machine, aforesaid substrate is washed 5 minutes, vapor deposition is sent to
In machine.CuPc is deposited in ITO first (anode) aboveAnd then NPB is depositedMain substance 4,4'-N, N'-
Two carbazole of biphenyl (" CBP ") and 001 95:5 weight ratio of dopant compound L mixing vapor depositionElectron-transport is deposited
Layer " Alq3 "Electron injecting layer LiF is depositedEvaporation cathode AlOrganic electroluminescence is prepared in form
Luminescent device.Performance characteristics of luminescence test to obtained device, measurement use 2400 type source measuring unit of KEITHLEY, CS-
2000 spectroradio luminance meters, to evaluate driving voltage, light emission luminance, luminous efficiency.
Referring to the above method, compound L 001 is replaced with into L012, L025, L039, L059, L065 respectively, is prepared
The organic electroluminescence device of respective compound.
Comparative example 1
Organic electroluminescence device is prepared according to the identical method of embodiment 7, luminescent layer doped compound structure is as follows:
Detection same as Example 7 is carried out to the organic electroluminescence device of preparation, the results are shown in Table 1.
Organic electroluminescence device testing result in 1 embodiment 7 of table and comparative example 1
Table 1 is as can be seen that use the present invention to provide iridium metal complex as organic prepared by luminescent layer dopant material
Electroluminescent device compound Ir (bty) 2acac compared with using is sent out as organic electroluminescence prepared by luminescent layer dopant material
Optical device is compared, and driving voltage is substantially reduced, and current efficiency, power efficiency and brightness are significantly improved.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (10)
1. a kind of iridium metal complex, which is characterized in that its structural formula as described in chemical formula 1:
Wherein: R1、R2、R3And R4It is each independently selected from hydrogen, deuterium, halogen, cyano, substituted or non-substituted C1-C6 alkyl, replaces
Or non-substituted C6-C18 aryl, substituted or non-substituted C4-C12 aromatic heterocyclic radical or substituted or non-substituted C8~C16
Condensed ring radical；
R1、R2、R3The position of substitution is any position of place ring；R1、R2The quantity of substituent group is 0~2, R3The quantity of substituent group
It is 0~4.
2. iridium metal complex according to claim 1, which is characterized in that the alkyl be straight chained alkyl, branched alkyl,
The branched alkyl or at least one substituent group of direct-connected alkyl, the substitution of at least one substituent group that naphthenic base, at least one substituent group replace
Substituted naphthenic base；Wherein, the substituent group is independent selected from one or more of halogen, deuterium, cyano, hydroxyl and sulfydryl.
3. iridium metal complex according to claim 1, which is characterized in that the aryl is for unsubstituted aryl or at least
The aryl that 1 substituent group replaces；Wherein, the substituent group is independent is selected from halogen, deuterium, amino, cyano, nitro, hydroxyl or mercapto
Base.
4. iridium metal complex according to claim 1, which is characterized in that the aromatic heterocyclic radical is unsubstituted heteroaryl
The aromatic heterocyclic radical that base or at least one substituent group replace；Wherein, the hetero atom in heteroaryl is nitrogen, sulphur or oxygen；The substituent group
It is independent to be selected from halogen, deuterium, amino, cyano, nitro, hydroxyl or sulfydryl.
5. iridium metal complex according to claim 1, which is characterized in that R1、R2、R3On independent and place ring
Other substituent groups mutually form substituted or non-substituted C3~C30 aliphatic ring, substituted or non-substituted C6~C60 aromatic ring, take
Generation or non-substituted C2~C60 heteroaromatic, substituted or non-substituted C6~C60 condensed ring or substituted or non-substituted C5~C60 spiral shell
Ring；
Or R1、R2、R3Between mutually form substituted or non-substituted C3~C30 aliphatic ring, substituted or non-substituted C6~
C60 aromatic ring, substituted or non-substituted C2~C60 heteroaromatic, substituted or non-substituted C6~C60 condensed ring or substituted or non-substituted
C5~C60 loop coil；
Substituent group on the aforementioned substituent group is at least selected from hydrogen, deuterium, halogen, cyano, substituted or non-substituted C1-C6 alkane
Base, substituted or non-substituted C6-C18 aryl, substituted or non-substituted C4-C12 aromatic heterocyclic radical, substituted or non-substituted C8~
One of the condensed ring radical of C16, substituted or non-substituted C5~C60 loop coil.
6. iridium metal complex according to claim 1, which is characterized in that it is selected from any one in flowering structure:
7. iridium metal complex according to claim 1, which is characterized in that it is selected from any one in flowering structure:
8. a kind of preparation method of iridium metal complex described in claim 1-7 any one, which is characterized in that including following
Step:
Step 1 sufficiently reacts raw material A with iridous chloride, and bridge ligand intermediate B is made；
Step 2 sufficiently reacts intermediate B with intermediate C, and iridium metal complex shown in chemical formula 1 is made；
Its synthetic route is as follows:
9. a kind of organic electroluminescence device comprising iridium metal complex described in claim 1-7 any one.
10. organic electroluminescence device according to claim 9, which is characterized in that it includes luminescent layer, the luminescent layer
Include iridium metal complex described in claim 1-7 any one.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818741A (en) * | 2019-11-15 | 2020-02-21 | 吉林奥来德光电材料股份有限公司 | Organic doped luminescent compound, preparation method thereof and organic electroluminescent device |
| CN111269269A (en) * | 2020-02-21 | 2020-06-12 | 吉林奥来德光电材料股份有限公司 | Iridium metal complex, preparation method thereof and organic electroluminescent device |
| CN111690019A (en) * | 2020-07-15 | 2020-09-22 | 奥来德(上海)光电材料科技有限公司 | Organic iridium metal complex and preparation method and application thereof |
| CN112028944A (en) * | 2020-09-07 | 2020-12-04 | 奥来德(上海)光电材料科技有限公司 | Organic iridium complex containing heteroatom, preparation method thereof and photoelectric device |
-
2019
- 2019-07-10 CN CN201910619237.0A patent/CN110330530A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818741A (en) * | 2019-11-15 | 2020-02-21 | 吉林奥来德光电材料股份有限公司 | Organic doped luminescent compound, preparation method thereof and organic electroluminescent device |
| CN111269269A (en) * | 2020-02-21 | 2020-06-12 | 吉林奥来德光电材料股份有限公司 | Iridium metal complex, preparation method thereof and organic electroluminescent device |
| CN111269269B (en) * | 2020-02-21 | 2022-04-01 | 吉林奥来德光电材料股份有限公司 | Iridium metal complex, preparation method thereof and organic electroluminescent device |
| CN111690019A (en) * | 2020-07-15 | 2020-09-22 | 奥来德(上海)光电材料科技有限公司 | Organic iridium metal complex and preparation method and application thereof |
| CN112028944A (en) * | 2020-09-07 | 2020-12-04 | 奥来德(上海)光电材料科技有限公司 | Organic iridium complex containing heteroatom, preparation method thereof and photoelectric device |
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