CN107286196A - A kind of organometallic complex as electroluminescent organic material - Google Patents
A kind of organometallic complex as electroluminescent organic material Download PDFInfo
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- CN107286196A CN107286196A CN201610194737.0A CN201610194737A CN107286196A CN 107286196 A CN107286196 A CN 107286196A CN 201610194737 A CN201610194737 A CN 201610194737A CN 107286196 A CN107286196 A CN 107286196A
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- 125000002524 organometallic group Chemical group 0.000 title claims abstract description 31
- 239000011368 organic material Substances 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 28
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- -1 heterocycle alkane Chemical class 0.000 claims abstract description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims abstract description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 150000001924 cycloalkanes Chemical class 0.000 claims abstract description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 4
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 4
- 125000004415 heterocyclylalkyl group Chemical group 0.000 claims abstract description 4
- 150000002431 hydrogen Chemical class 0.000 claims abstract 3
- 229910052741 iridium Inorganic materials 0.000 claims description 11
- 125000005842 heteroatom Chemical group 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 230000005525 hole transport Effects 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 18
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 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 6
- 238000010792 warming Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 4
- 238000005401 electroluminescence Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 238000001698 laser desorption ionisation Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 3
- 229910006400 μ-Cl Inorganic materials 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000011521 glass 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
- 238000011160 research Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- HTFNVAVTYILUCF-UHFFFAOYSA-N 2-[2-ethoxy-4-[4-(4-methylpiperazin-1-yl)piperidine-1-carbonyl]anilino]-5-methyl-11-methylsulfonylpyrimido[4,5-b][1,4]benzodiazepin-6-one Chemical compound CCOc1cc(ccc1Nc1ncc2N(C)C(=O)c3ccccc3N(c2n1)S(C)(=O)=O)C(=O)N1CCC(CC1)N1CCN(C)CC1 HTFNVAVTYILUCF-UHFFFAOYSA-N 0.000 description 1
- IYGHCHIIHDHCIJ-UHFFFAOYSA-N CC(C1)C1S(N)I Chemical compound CC(C1)C1S(N)I IYGHCHIIHDHCIJ-UHFFFAOYSA-N 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides a kind of organometallic complex as electroluminescent organic material, its structure is as follows：Wherein, A is selected from substituted or unsubstituted five yuan or hexa-atomic cycloalkane or aromatic hydrocarbons, or contains one or more heteroatomic substituted or unsubstituted five yuan or hexa-member heterocycle alkane or heteroaryl hydrocarbon；X1、X2、Y1And Y2For CR ' or N, and X1And X2It is identical, Y1And Y2It is identical, X1And Y1It is different；R ' and R1It is independently selected from hydrogen, deuterium, halogen, alkyl group, substituted or unsubstituted cycloalkyl, substituted or unsubstituted Heterocyclylalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl.The organometallic complex is mainly used in the luminescent layer of OLED, it is preferable that applied in feux rouges guest materials, the beneficial effect such as obtained device has low long lifespan, driving voltage, chemical stability and heat endurance is good.
Description
Technical field
The present invention relates to a kind of metal complex, more particularly to a kind of organometallic ligand as electroluminescent organic material
Compound.
Background technology
TFT-LCD, as a kind of display screen, is a kind of display of non-spontaneous light, it is necessary to pass through backlight throw light,
Sequentially penetrate the phases such as Polarizer, glass substrate, liquid crystal layer, colored filter, glass substrate, Polarizer in TFT-LCD panels
Spare part is closed, eye imaging is finally entered, reaches the function of display.In actual applications, TFT-LCD display screens have reaction
Speed is slow, power consumption, narrow viewing angle the shortcomings of, be not enough to turn into perfect display screen.
Organic electroluminescent refers to the thin-film device being prepared into by organic photoelectric functional material under the excitation of electric field
Luminous phenomenon, is described as most potential flat panel display of future generation by industrial circle and academia, is regarded with low-power consumption, width
Angle, respond it is fast, lighter and thinner and can Flexible Displays the advantages of.Organic electroluminescence device is also known as Organic Light Emitting Diode
(OLED), it is made up of transparent anode ITO, metallic cathode and organic thin film layer.Under direct voltage drive, negative electrode injected electrons
Move, finally met in luminescent layer and recombination luminescence to organic luminous layer with anode injected holes.With inorganic semiconductor two
Pole pipe is compared, organic semiconductor diodes due to the randomness of its structure, the diversity of material and cause carrier physics mistake
Journey seems increasingly complex, and the organic material for electron transfer layer and hole blocking layer is most important.
Electroluminescent organic material has as the core component of organic electroluminescence device to the performance of device
Have a great impact.Wherein, the fluorescent characteristic of high-quantum efficiency, good characteristic of semiconductor, high-quality film forming characteristics, good
Chemical stability and heat endurance, good processing characteristics etc. be its main performance factors.According to molecular structure property with
Emission wavelength range is classified, including small molecular organic compounds, organic coordination compound luminescent material and organic polymer material.
Wherein, CN104650040A discloses a kind of organic electroluminescent compounds of azophenlyene analog derivative, its structural formula
For：Wherein, the organic electroluminescent compounds are used at least luminescent layer, hole injection layer, hole
It is good with electroluminescent efficiency in one layer or several layers of in transport layer, hole blocking layer, electron injecting layer or electron transfer layer
With excitation is excellent and advantage of long lifespan；CN104744369A discloses a kind of electroluminescent organic material, and it contains knot
Structure formula isDerivative；Wherein, the derivative forms class loop coil due to having introduced 2 phenyl ring
The material of compound, adds the planar conjugate of molecular structure, improves the dissolubility of such electroluminescent organic material, makes
It is easier to prepare, meanwhile, such electroluminescent organic material can change the transition of electronics due to the introducing of different substituents,
Adjust its luminous peak position, in the preparation of blue-light device, the need for industrialized production being met.
At present, constantly expand with the application of organic electroluminescence device, those skilled in the art are for Organic Electricity
The research of electroluminescent material is also deepening continuously, nevertheless, luminescent material in actual application there are still it is many not
Foot, therefore, is designed with synthesizing a kind of new Organic Electro Luminescent Materials to overcome the shortcomings of to occur during current practice,
It is the emphasis in OLED research work.
The content of the invention
Based on above-mentioned background technology, the invention provides a kind of organic metal cooperation as electroluminescent organic material
Thing, is mainly used in the luminescent layer of OLED, it is preferable that applied in feux rouges guest materials, obtained device has the longevity
Order length, low driving voltage, chemical stability and the beneficial effect such as heat endurance is good.
Technical scheme includes a kind of organometallic complex as electroluminescent organic material, and its structure is such as
Shown in logical formula (I)：
Wherein, A is selected from substituted or unsubstituted five yuan or hexa-atomic cycloalkane or aromatic hydrocarbons, or contains one or more miscellaneous originals
Substituted or unsubstituted five yuan or hexa-member heterocycle alkane or heteroaryl hydrocarbon of son；
X1、X2、Y1And Y2For CR ' or N, and X1And X2It is identical, Y1And Y2It is identical, X1And Y1It is different；
R ' and R1It is independently selected from hydrogen, deuterium, halogen, alkyl group, substituted or unsubstituted cycloalkyl, substitution or does not take
The Heterocyclylalkyl in generation, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl；
M is the metal that atomic weight is more than 40；
T is assistant ligand；
M be metal M total ligancy, n for less than m and at least 1 integer.
In one embodiment of the invention, the M is Ir.
In another embodiment, T structure is
Further, in one embodiment, n is 2.
In one embodiment of the invention, A selected from heterocycloalkane or heteroaryl hydrocarbon in hetero atom number be no more than 2,
And hetero atom species is also no more than two, the hetero atom is selected from N, O or S.Further, it is described to be substituted by mono-, di-, three, four
Or five substitution, substituent is preferably hydrogen or alkyl group, more preferably methyl.
In one embodiment, R ' is selected from hydrogen, alkyl group, preferably methyl, ethyl.
In another embodiment, R1Mono-, di- or three substituents are represented, hydrogen, alkyl group, more preferably first preferably is selected from
Base, ethyl.
In a preferred embodiment of the invention, the structure of the organometallic complex is as follows：
Technical scheme also includes a kind of organic electroluminescence material containing organometallic complex described above
Material.
Technical scheme also include a kind of OLED emitting layer materials containing organometallic complex described above,
Electron transport layer materials or hole transport layer material.
Technical scheme also includes a kind of OLED feux rouges object materials containing organometallic complex described above
Material.
Technical scheme also includes a kind of OLED containing organometallic complex described above.
Embodiment
The invention provides a kind of organometallic complex as electroluminescent organic material, its structure such as logical formula (I)
It is shown：
Wherein, A is selected from substituted or unsubstituted five yuan or hexa-atomic cycloalkane or aromatic hydrocarbons, or contains one or more miscellaneous originals
Substituted or unsubstituted five yuan or hexa-member heterocycle alkane or heteroaryl hydrocarbon of son；
X1、X2、Y1And Y2For CR ' or N, and X1And X2It is identical, Y1And Y2It is identical, X1And Y1It is different；
R ' and R1It is independently selected from hydrogen, deuterium, halogen, alkyl group, substituted or unsubstituted cycloalkyl, substitution or does not take
The Heterocyclylalkyl in generation, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl；
M is the metal that atomic weight is more than 40；
T is assistant ligand；
M be metal M total ligancy, n for less than m and at least 1 integer.
In one embodiment of the invention, the M is Ir.
In another embodiment, T structure is
Further, in one embodiment, n is 2.
In one embodiment of the invention, A selected from heterocycloalkane or heteroaryl hydrocarbon in hetero atom number be no more than 2,
And hetero atom species is also no more than two, the hetero atom is selected from N, O or S.Further, it is described to be substituted by mono-, di-, three, four
Or five substitution, substituent is preferably hydrogen or alkyl group, more preferably methyl.
In one embodiment, R ' is selected from hydrogen, alkyl group, preferably methyl, ethyl.
In another embodiment, R1Mono-, di- or three substituents are represented, hydrogen, alkyl group, more preferably first preferably is selected from
Base, ethyl.
In a preferred embodiment of the invention, the structure of the organometallic complex is as follows：
Present invention also offers a kind of electroluminescent organic material containing organometallic complex described above.
Present invention also offers a kind of OLED emitting layer materials containing organometallic complex described above, electric transmission
Layer material or hole transport layer material.
Present invention also offers a kind of OLED feux rouges guest materials containing organometallic complex described above.
Present invention also offers a kind of OLED containing organometallic complex described above.
According to the above-mentioned technical proposal of the present invention, now by embodiment and Application Example in detail below, to this hair
Bright content is further explained and illustrated.
Embodiment 1
A kind of organometallic complex, with the structure shown in formula (1), may be used as electroluminescent organic material, especially
It is applied to feux rouges guest materials：
Its synthetic method is：
(1) preparation of ligand L 1
Weigh Compound A1 (5mmol) and compound B (6mmol) are added in three-necked flask, add Pd2(dba)3Make
- inflated with nitrogen-for catalyst, is vacuumized on biexhaust pipe to vacuumize, and is circulated three times, is finally protected reaction system with nitrogen.With note
Emitter adds the THF solution 25mL of cesium carbonate, and 4h or so is reacted at 105 DEG C, room temperature is cooled to.Post purification is crossed after revolving, is obtained
To solid product L1.
(1) preparation of complex 1
Weigh IrCl3·3H2O (1mmol) and L1 (2.5mmol) are added in three-necked flask, vacuumized on biexhaust pipe-
Inflated with nitrogen-vacuumize, circulates three times, finally protects reaction system with nitrogen.By the mixture (3 of cellosolvo and water:1,
V/v) it is injected into reaction system, is stirred with syringe, and reaction system is warming up to 110 DEG C, the reaction time is 24 hours left sides
There is precipitation to generate in the right side, course of reaction.Reaction system is cooled to room temperature, then precipitation is filtered, and is washed with water, ethanol, is obtained
To red solid product, i.e. iridium dichloro bridge compounds (L1)2Ir(μ-Cl)2Ir(L1)2。
Weigh iridium dichloro bridge compounds (0.2mmol) and Na2CO3(1.4mmol) is simultaneously added in three-necked flask, double
- inflated with nitrogen-is vacuumized on pipe to vacuumize, and is circulated three times, is finally protected reaction system with nitrogen.With syringe into reaction system
Acetylacetone,2,4-pentanedione (0.5mmol) and cellosolvo are injected separately into, is stirred, and reaction system is warming up to backflow.Reaction is carried out
After 12 hours, reactant mixture is down to room temperature, red precipitate is filtrated to get, post purification is crossed with column chromatography method, obtains red
Color solid complexes 1.
When the structure of gained complex of iridium is by laser desorption ionization m- flight mass spectrometer (MALDI-TOF-MASS) and
Proton nmr spectra (1H NMR) is analyzed.
Molecular weight characterization MS 881.92
1H-NMR：(400MHz, CDCl3), δ (ppm)：9.22(s,2H),8.76(s,2H),7.72(s,2H),7.58(d,
2H),7.44(d,2H),7.31-7.38(m,10H),7.00-7.12(m,4H),4.61(s,1H),1.45(s,6H).
Embodiment 2
A kind of organometallic complex, with the structure shown in formula (3), may be used as electroluminescent organic material, especially
It is applied to feux rouges guest materials：
Its synthetic method is：
(1) preparation of ligand L 3
Weigh Compound A3 (5mmol) and compound B (6mmol) are added in three-necked flask, add Pd2(dba)3Make
- inflated with nitrogen-for catalyst, is vacuumized on biexhaust pipe to vacuumize, and is circulated three times, is finally protected reaction system with nitrogen.With note
Emitter adds the THF solution 25mL of cesium carbonate, and 4h or so is reacted at 105 DEG C, room temperature is cooled to.Post purification is crossed after revolving, is obtained
To solid product L3.
(2) preparation of complex 3
Weigh IrCl3·3H2O (1mmol) and L3 (2.5mmol) are added in three-necked flask, vacuumized on biexhaust pipe-
Inflated with nitrogen-vacuumize, circulates three times, finally protects reaction system with nitrogen.By the mixture (3 of cellosolvo and water:1,
V/v) it is injected into reaction system, is stirred with syringe, and reaction system is warming up to 110 DEG C, the reaction time is 24 hours left sides
There is precipitation to generate in the right side, course of reaction.Reaction system is cooled to room temperature, then precipitation is filtered, and is washed with water, ethanol, is obtained
To red solid product, i.e. iridium dichloro bridge compounds (L3)2Ir(μ-Cl)2Ir(L3)2。
Weigh iridium dichloro bridge compounds (0.2mmol) and Na2CO3(1.4mmol) is simultaneously added in three-necked flask, double
- inflated with nitrogen-is vacuumized on pipe to vacuumize, and is circulated three times, is finally protected reaction system with nitrogen.With syringe into reaction system
Acetylacetone,2,4-pentanedione (0.5mmol) and cellosolvo are injected separately into, is stirred, and reaction system is warming up to backflow.Reaction is carried out
After 12 hours, reactant mixture is down to room temperature, red precipitate is filtrated to get, post purification is crossed with column chromatography method, obtains red
Color solid complexes 3.
When the structure of gained complex of iridium is by laser desorption ionization m- flight mass spectrometer (MALDI-TOF-MASS) and
Proton nmr spectra (1H NMR) is analyzed.
Molecular weight characterization MS 910.12
1H-NMR：(400MHz, CDCl3), δ (ppm)：9.25(s,2H),8.76(s,2H),7.74(s,2H),7.41(d,
2H),7.31-7.38(m,10H),6.68-6.71(m,4H),4.68(s,1H),1.51(s,6H).
Embodiment 3
A kind of organometallic complex, with the structure shown in formula (10), may be used as electroluminescent organic material, especially
It is applied to feux rouges guest materials：
Its synthetic method is：
(1) preparation of ligand L 10
Weigh Compound A10 (5mmol) and compound B (6mmol) are added in three-necked flask, add Pd2(dba)3Make
- inflated with nitrogen-for catalyst, is vacuumized on biexhaust pipe to vacuumize, and is circulated three times, is finally protected reaction system with nitrogen.With note
Emitter adds the THF solution 25mL of cesium carbonate, and 4h or so is reacted at 105 DEG C, room temperature is cooled to.Post purification is crossed after revolving, is obtained
To solid product L10.
(2) preparation of complex 10
Weigh IrCl3·3H2O (1mmol) and L10 (2.5mmol) are added in three-necked flask, vacuumized on biexhaust pipe-
Inflated with nitrogen-vacuumize, circulates three times, finally protects reaction system with nitrogen.By the mixture (3 of cellosolvo and water:1,
V/v) it is injected into reaction system, is stirred with syringe, and reaction system is warming up to 110 DEG C, the reaction time is 24 hours left sides
There is precipitation to generate in the right side, course of reaction.Reaction system is cooled to room temperature, then precipitation is filtered, and is washed with water, ethanol, is obtained
To red solid product, i.e. iridium dichloro bridge compounds (L10)2Ir(μ-Cl)2Ir(L10)2。
Weigh iridium dichloro bridge compounds (0.2mmol) and Na2CO3(1.4mmol) is simultaneously added in three-necked flask, double
- inflated with nitrogen-is vacuumized on pipe to vacuumize, and is circulated three times, is finally protected reaction system with nitrogen.With syringe into reaction system
Acetylacetone,2,4-pentanedione (0.5mmol) and cellosolvo are injected separately into, is stirred, and reaction system is warming up to backflow.Reaction is carried out
After 12 hours, reactant mixture is down to room temperature, red precipitate is filtrated to get, post purification is crossed with column chromatography method, obtains red
Color solid complexes 10.
When the structure of gained complex of iridium is by laser desorption ionization m- flight mass spectrometer (MALDI-TOF-MASS) and
Proton nmr spectra (1H NMR) is analyzed.
Molecular weight characterization MS 857.86
1H-NMR：(400MHz, CDCl3), δ (ppm)：9.25(s,2H),8.76(s,2H),7.72(s,2H),7.62(d,
2H),7.45(d,2H),7.00-7.12(m,4H),6.46-6.52(m,6H),4.61(s,1H),2.83(d,4H),1.45(s,
6H).
Application Example
Contrast Application Example
Transparent anode electrode ito substrate is cleaned by ultrasonic 5-10 minutes in isopropanol, and exposes 20-30 under ultraviolet light
Minute, then handled 5-10 minutes with plasma.The ito substrate after processing is then put into evaporated device.One layer is deposited first
30-50nm NPB is as hole transmission layer, followed by the evaporation of luminescent layer, mixing evaporation compound CBP, and 5--10%
Ir (piq) 2 (acac), is then deposited 20-40nm Alq3 as electron transfer layer, 0.5-2nmLiF is then deposited again, then
100-200nm metal Al is deposited.
Device Application Example 1
Transparent anode electrode ito substrate is cleaned by ultrasonic 5-10 minutes in isopropanol, and exposes 20-30 under ultraviolet light
Minute, then handled 5-10 minutes with plasma.The ito substrate after processing is then put into evaporated device.One layer is deposited first
30-50nm NPB is as hole transmission layer, followed by the evaporation of luminescent layer, mixing evaporation compound CBP, and 5-10%
The Alq3 of complex 1, then evaporation 20-40nm, is then deposited 0.5-2nmLiF again, then evaporation 100-200nm metal Al.
Device Application Example 2
Change the complex Ir (piq) 2 (acac) in comparative example into complexs 3, be used as luminescent layer object.
Device Application Example 3
Change the complex Ir (piq) 2 (acac) in comparative example into complexs 10, be used as luminescent layer object.
Wherein,
The OLED structure of each Application Example is as follows：
Contrast Application Example：ITO/NPB/CBP：Ir(piq)2(acac)/Alq3/LiF/Al；
Device Application Example 1：ITO/NPB/CBP：Complex 1/Alq3/LiF/Al；
Device Application Example 2：ITO/NPB/CBP：Complex 3/Alq3/LiF/Al；
Device Application Example 3：ITO/NPB/CBP：Complex 10/Alq3/LiF/Al.
Under 1000nits, OLED result such as following table one：
Table one
| Application Example | Voltage/V | Cd/A | lm/W | CIEx | CIEy | LT90@1000nit |
| 1 | 4.7 | 15 | 11.8 | 0.670 | 0.325 | 119 |
| 2 | 5.1 | 18 | 13.6 | 0.670 | 0.330 | 131 |
| 3 | 4.8 | 16 | 12.3 | 0.669 | 0.328 | 125 |
| Comparative example | 5.3 | 14 | 10.3 | 0.670 | 0.330 | 108 |
Data explanation listed by above-mentioned table one, compared to Comparison study embodiment, to include chemical combination of the embodiment of the present invention
Driving voltage made from the material of thing needed for luminescent device is lower, more efficient.
The specific embodiment of the present invention is described in detail above, but it is intended only as example, and the present invention is not limited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
Substitute also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should be contained within the scope of the invention.
Claims (10)
1. a kind of organometallic complex as electroluminescent organic material, it is characterised in that its structure is as led to formula (I) institute
Show：
Wherein, A is selected from substituted or unsubstituted five yuan or hexa-atomic cycloalkane or aromatic hydrocarbons, or containing one or more heteroatomic
Substituted or unsubstituted five yuan or hexa-member heterocycle alkane or heteroaryl hydrocarbon；
X1、X2、Y1And Y2For CR ' or N, and X1And X2It is identical, Y1And Y2It is identical, X1And Y1It is different；
R ' and R1Be independently selected from hydrogen, it is deuterium, halogen, alkyl group, substituted or unsubstituted cycloalkyl, substituted or unsubstituted
Heterocyclylalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl；
M is the metal that atomic weight is more than 40；
T is assistant ligand；
M be metal M total ligancy, n for less than m and at least 1 integer.
2. organometallic complex according to claim 1, it is characterised in that the M is Ir, and n is 2.
3. organometallic complex according to claim 1, it is characterised in that T structure is
4. organometallic complex according to claim 1, it is characterised in that A selected from heterocycloalkane or heteroaryl hydrocarbon in
Hetero atom number be no more than 2, and hetero atom species also be no more than two, the hetero atom be selected from N, O or S.
5. organometallic complex according to claim 1, it is characterised in that be substituted by mono-, di-, three, four described in A
Or five substitution, substituent be hydrogen or alkyl group.
6. organometallic complex according to claim 1, it is characterised in that R1Mono-, di- or three substituents are represented, are selected from
Hydrogen, alkyl group.
7. organometallic complex according to claim 1, it is characterised in that the structure of the organometallic complex is such as
Under：
8. OLED emitting layer materials, the electronics of the organometallic complex in a kind of 1-7 containing claim described in any one
Transmit layer material or hole transport layer material.
9. a kind of OLED feux rouges guest materials of the organometallic complex in 1-7 containing claim described in any one.
10. a kind of OLED of the organometallic complex in 1-7 containing claim described in any one.
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| CN114163480A (en) * | 2021-10-26 | 2022-03-11 | 奥来德(上海)光电材料科技有限公司 | Organic iridium metal complex with long service life and high efficiency and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070196687A1 (en) * | 2004-03-31 | 2007-08-23 | Konica Minolta Holding, Inc. | Organic Electroluminescence Element Material, Organic Electroluminescence Element,Display Device And Illumination Device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20070196687A1 (en) * | 2004-03-31 | 2007-08-23 | Konica Minolta Holding, Inc. | Organic Electroluminescence Element Material, Organic Electroluminescence Element,Display Device And Illumination Device |
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| CN114163480A (en) * | 2021-10-26 | 2022-03-11 | 奥来德(上海)光电材料科技有限公司 | Organic iridium metal complex with long service life and high efficiency and application thereof |
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