CN118724969A - Metal platinum (II) complex containing imidazole structural unit and application thereof - Google Patents
Metal platinum (II) complex containing imidazole structural unit and application thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 31
- 239000002184 metal Substances 0.000 title claims abstract description 31
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 27
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 36
- 239000010410 layer Substances 0.000 claims description 35
- 239000002019 doping agent Substances 0.000 claims description 20
- 229910052697 platinum Inorganic materials 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052805 deuterium Inorganic materials 0.000 claims description 10
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002346 layers by function Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- -1 deuterium hydrogen Chemical group 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 230000005693 optoelectronics Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 239000004305 biphenyl Chemical group 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims 1
- 238000013086 organic photovoltaic Methods 0.000 claims 1
- 108091008695 photoreceptors Proteins 0.000 claims 1
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- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 57
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000003446 ligand Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- REAYFGLASQTHKB-UHFFFAOYSA-N [2-[3-(1H-pyrazol-4-yl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound N1N=CC(=C1)C=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 REAYFGLASQTHKB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000003057 platinum Chemical class 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- DIVZFUBWFAOMCW-UHFFFAOYSA-N 4-n-(3-methylphenyl)-1-n,1-n-bis[4-(n-(3-methylphenyl)anilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 DIVZFUBWFAOMCW-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical group [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229940081066 picolinic acid Drugs 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 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 2
- 238000000862 absorption spectrum Methods 0.000 description 1
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- 229920002457 flexible plastic Polymers 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- 230000031700 light absorption Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the technical field of metal organic luminescent materials, in particular to a metal platinum (II) complex containing an imidazole structural unit and application thereof. The structure of the complex is shown as a general formula (I):
Description
Technical Field
The invention relates to the technical field of metal organic luminescent materials, in particular to a metal platinum (II) complex containing an imidazole structural unit and application thereof.
Background
Organic Light Emitting Diodes (OLEDs) are a new generation of full color display and lighting technologies. The OLED is an autonomous light emitting device, a backlight source is not needed, and energy is saved; the device has the advantages of low driving voltage, high response speed, high resolution and contrast, wide viewing angle, wide use temperature range and the like; the display device can also be prepared by taking cheap glass and flexible plastic as substrates. In addition, the method has the advantages of low cost, simple production process, large-area production and the like. Therefore, the OLED has wide and huge application prospect in the aspects of high-end electronic products and aerospace; and there is also a huge potential market in the area of planar solid state lighting. Phosphorescent metal complexes are currently a good choice of dopants in the emissive layer of OLEDs and have gained great attention in both academic and industrial fields. OLEDs have been used for advanced displays for smartphones, televisions and digital cameras with a number of achievements.
The design and development of luminescent materials is the core of the OLED field. At present, heavy metal phosphorescence organic complex molecules capable of meeting commercial application are basically cyclometallated iridium (III) complex molecules, but the price of the metal iridium is high, and the quantity of the metal iridium is limited. The content of the metal platinum element in the crust and annual output in the world are about ten times of that of the metal iridium element, the relative price is low, in addition, the total yield of the iridium (III) complex phosphorescent material is low, and the preparation cost of the iridium (III) complex phosphorescent material is further improved. In contrast, the platinum (II) complex phosphorescent material has high platinum element utilization rate in the preparation process, and the preparation cost of the platinum (II) complex phosphorescent material is far lower than that of the iridium (III) complex phosphorescent material.
The cyclometalated platinum (II) complex based on the bidentate ligand has low molecular rigidity, and the two bidentate ligands are easy to distort and vibrate to cause non-radiation attenuation, so that the phosphorescence quantum efficiency is low; however, the cyclometallated platinum (II) complex molecules based on tridentate ligands require a second complexing ion (e.g., alkyne anions, cl-, carbenes, etc.), which also results in reduced chemical and thermal stability of the complex; thereby affecting its application as a phosphorescent material in OLED devices. In contrast, the cyclometalated platinum (II) complex based on the tetradentate ligand has strong molecular rigidity, high radiation luminous rate and greatly improved quantum efficiency, and simultaneously has higher chemical stability and thermal stability, thereby being an ideal molecule for developing novel OLED phosphorescent materials. The development of a novel stable and efficient phosphorescent material still has important significance for the development of OLED industry.
Disclosure of Invention
Accordingly, it is an object of the present invention to provide a platinum (II) complex containing an imidazole structural unit. When the metal platinum (II) complex containing the imidazole structural unit is used as a luminescent material of an OLED device, the luminescent efficiency of the device is greatly improved, and meanwhile, the service life of the device is obviously prolonged.
The technical scheme of the invention is as follows:
The invention provides a metal platinum (II) complex containing imidazole structural unit, the structure of the complex is shown as a general formula (I):
Wherein Ar 1 is hydrogen or phenyl;
Ar 2-Ar3 is any of the following formulae:
Wherein R 1、R2、R3、R4 is each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C18 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkylthio, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C30 aryl;
R 5 is selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C18 alkyl, substituted or unsubstituted C6-C30 aryl;
all groups may be partially deuterated or fully deuterated and when a substituent is present, the substitution may be one or more times; the substituents are optionally selected from one or more of hydrogen, deuterium, F, C-C18 alkyl, C6-C30 aryl.
Further preferably, each R 1、R2、R3、R4 is independently selected from the group consisting of hydrogen, deuterium hydrogen, -F, cyano, phenyl, biphenyl, C1-C18 alkyl, C3-C10 cycloalkyl 、-CD3、-CD2H、-CDH2、-CF3、-CF2H、-CFH2、-OCH3、-OCDH2、-OCD2H、-OCD3、-SCH3、-SCDH2、-SCD2H、-SCD3.
Preferably, each R 1、R2、R3、R4 is independently selected from the group represented by the following formula, wherein at least one hydrogen may be substituted by deuterium:
Wherein "×" indicates the position to be fused.
More preferably, the metal platinum complex according to the present invention is selected from any one of the chemical structures shown below:
In one aspect, the invention also provides application of the metal platinum complex with the general structure shown in the formula (I) in an organic electroluminescent device.
In another aspect, the invention also provides an organic electroluminescent device, which comprises the metal platinum complex with the general structure shown in the formula (I).
Further, the organic electroluminescent device comprises a cathode, an anode and an organic functional layer between the cathode and the anode; the organic functional layer comprises a light-emitting layer, and the light-emitting layer comprises a metal platinum complex with a general structure shown in the formula (I).
In another aspect, the present invention provides an organic optoelectronic device comprising a first electrode; a second electrode facing the first electrode; and a luminescent material layer arranged between the first electrode and the second electrode, wherein the luminescent material layer comprises a metal platinum complex with a general structure shown in the formula (I). For example, a metal platinum complex may be included as a dopant in the light emitting material layer.
The invention also provides a composition which comprises the metal platinum complex with the general structure shown in the formula (I).
The invention also provides a preparation which comprises the metal platinum complex with the general structure shown in the formula (I) or the composition and at least one solvent.
The invention also provides a display or lighting device comprising one or more of the organic electroluminescent devices as described above.
Compared with the prior art, the invention has the beneficial effects that:
The strong spin orbit coupling of the platinum metal atoms between the singlet state and the triplet state excited state effectively enhances intersystem crossing, shows the potential of utilizing the singlet state and the triplet state excitons simultaneously, realizes 100% internal quantum efficiency, and further improves the luminous efficiency of the device. The platinum metal complex shown in the formula (I) is used as a doping agent to be applied to a luminescent layer to prepare an organic luminescent device, and the obtained device has good improvement on luminous efficiency and service life, and is an organic luminescent material with good performance.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the claims.
The compounds disclosed herein are metal platinum complexes. The term compound or complex is used interchangeably herein. The metal platinum complexes of the present invention are illustrated by, but not limited to, the platinum complexes and synthetic methods illustrated by the following examples. The disclosed compounds may exhibit desirable properties and have emission and/or absorption spectra that may be modulated by the selection of suitable ligands. In another aspect, the invention may exclude any one or more of the compounds, structures or portions thereof specifically recited in the invention.
Fluorescent emitters are a group of atoms in an organic molecule that can absorb energy to produce singlet excited states, which decay rapidly to produce instant luminescence. In one aspect, the complexes of the invention can provide emission in a substantial portion of the visible spectrum. In a specific example, the complex of the present invention can emit light in the wavelength band of visible light or near infrared light. On the other hand, the complexes of the invention have improved stability and efficiency over conventional complexes.
The complexes provided by the present invention are suitable for use in a wide variety of optical and electro-optical devices including, but not limited to, light absorbing devices such as solar and light sensing devices, organic light emitting diodes, light emitting devices or devices compatible with light absorption and emission. For example, it can be used as a doping material in the light emitting layer of an OLED to increase the light emitting efficiency and its device lifetime.
Example 1: synthesis of Compound 1-1
1-1-1 (18.3 MmoL,6.4 g) and 1-1-2 (22.0 mmoL,5.7 g) were dissolved and CuI (5.5 mmoL,1.1 g) and K 3PO4 (55.3 mmoL,11.7 g) and picolinic acid (27.5 mmoL,3.3 g) were added after dissolution in dimethyl sulfoxide (140 ml) and refluxed at 100℃for 12 hours. After the completion of the reaction, the reaction was cooled to room temperature, the organic layer was extracted with a mixture of ethyl acetate and water, washed with water 3 times, dried over magnesium sulfate, and then the solvent was removed under reduced pressure to obtain a crude product. Silica gel column chromatography (eluent: ethyl acetate: hexane) was performed on water to obtain the objective compound 1-1-3 (9.0 g, yield 68%). LC-MS: M/Z528 (M+).
To a 1000mL dry three-necked flask equipped with a magnetic rotor and a condenser were successively added 1-1-3 (6.8 g,12.9mmoL,6.8 g), potassium chloroplatinite (13.5 mmoL,5.6 g), tetrabutyl bromide Hua An (1.29 mmoL,0.42 g), nitrogen was purged three times, and acetic acid (500 mL) pre-purged with nitrogen was added. After the reaction solution was bubbled for 30 minutes, the mixture was stirred at room temperature for 12 hours, then the reaction was stirred at 120℃for 2 days, cooled to room temperature, the solvent was distilled off under reduced pressure, stannous chloride (25.8 mmoL,4.89 g) and methylene chloride (500 mL) were added, and the mixture was stirred at room temperature for 1 day. The reaction solution was washed with water, the aqueous phase was extracted three times with methylene chloride, the organic phases were combined, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography (petroleum ether/methylene chloride=3 to 1:1) to obtain the objective compound 1-1 (4.7 g, yield 50%). LC-MS: M/Z721 (M+).
Example 2: synthesis of Compounds 1-6
Synthesis of Compound 1-6 by the method for synthesizing Compound 1-1 in reference example 1 gave Compound 1-6 (5.4 g, yield 53%). LC-MS: M/Z787 (M+).
Example 3: synthesis of Compounds 1-81
1-81-1 (18.3 MmoL,7.2 g) and 1-81-2 (22.0 mmoL,6.4 g) were dissolved and CuI (5.5 mmoL,1.1 g) and K 3PO4 (55.3 mmoL,11.7 g) and picolinic acid (27.5 mmoL,3.3 g) were added after dissolution in dimethyl sulfoxide (140 ml) and refluxed at 100℃for 12 hours. After the completion of the reaction, the reaction was cooled to room temperature, the organic layer was extracted with a mixture of ethyl acetate and water, washed with water 3 times, dried over magnesium sulfate, and then the solvent was removed under reduced pressure to obtain a crude product. Silica gel column chromatography (eluent: ethyl acetate: hexane) was performed on water to obtain the objective compound 1-81-3 (6.5 g, yield 59%). LC-MS: M/Z602 (M+).
To a 1000mL dry three-necked flask equipped with a magnetic rotor and a condenser were successively added 1-81-3 (7.8 g,12.9mmoL,6.8 g), potassium chloroplatinite (13.5 mmoL,5.6 g), tetrabutyl bromide Hua An (1.29 mmoL,0.42 g), nitrogen was purged three times, and acetic acid (500 mL) pre-purged with nitrogen was added. After the reaction solution was bubbled for 30 minutes, the mixture was stirred at room temperature for 12 hours, then the reaction was stirred at 120℃for 2 days, cooled to room temperature, the solvent was distilled off under reduced pressure, stannous chloride (25.8 mmoL,4.89 g) and methylene chloride (500 mL) were added, and the mixture was stirred at room temperature for 1 day. The reaction solution was washed with water, the aqueous phase was extracted three times with methylene chloride, the organic phases were combined, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography (petroleum ether/methylene chloride=3 to 1:1) to obtain the objective compound 1-81 (5.5 g, yield 55%). LC-MS: M/Z795 (M+).
Example 4: synthesis of Compounds 1-261
Compounds 1 to 261 were synthesized by the synthesis method of the compounds 1 to 81 in reference example 3 to give compounds 1 to 261 (5.2 g, yield 52%). LC-MS: M/Z778 (M+).
Example 5: synthesis of Compounds 1-283
Synthesis of 1-283 by the method for synthesizing compound 1-1 in reference example 1 gave 1-283 (6.0 g, yield 61%). LC-MS: M/Z764 (M+).
Example 6: synthesis of Compounds 1-288
Compounds 1 to 288 were synthesized by the synthesis method of the compounds 1 to 81 in reference example 3, to give compounds 1 to 288 (5.6 g, yield 54%). LC-MS: M/Z796 (M+).
Example 7: synthesis of Compounds 1-315
Compounds 1 to 315 were synthesized by the synthesis method of the compound 1-1 in reference example 1 to give compounds 1 to 315 (6.3 g, yield 59%). LC-MS: M/Z827 (M+).
Example 8: synthesis of Compounds 2-14
Synthesis of Compound 2-14 by the method for synthesizing Compound 1-1 in reference example 1 gave Compound 2-14 (5.0 g, yield 56%). LC-MS: M/Z689 (M+).
Example 9: synthesis of Compound 2-21
Compounds 2 to 21 were synthesized by the synthesis method of the compounds 1 to 81 in reference example 3, to give compounds 2 to 21 (4.8 g, yield 49%). LC-MS: M/Z753 (M+).
Example 10: synthesis of Compounds 2-50
Synthesis of Compound 2-50 by the method for synthesizing Compound 1-1 in reference example 1 gave Compound 2-50 (5.7 g, yield 57%). LC-MS: M/Z770 (M+).
Example 11: synthesis of Compounds 2-66
Synthesis of Compound 2-66 by the method for synthesizing Compound 1-1 in reference example 1 gave Compound 2-66 (5.3 g, yield 54%). LC-MS: M/Z763 (M+).
Example 12: synthesis of Compounds 2-107
Compounds 2 to 107 were synthesized by the synthesis method of the compound 1-1 in reference example 1, to give compounds 2 to 107 (4.9 g, yield 52%). LC-MS: M/Z735 (M+).
Example 13: synthesis of Compound 2-171
Synthesis of Compound 2-171 by the method for synthesizing Compound 1-81 in reference example 3 gave Compound 2-171 (6.7 g, yield 65%). LC-MS: M/Z799 (M+).
Example 14: synthesis of Compounds 2-180
Synthesis of Compound 2-180 by the method for synthesizing Compound 1-1 in reference example 1 gave Compound 2-180 (6.7 g, yield 59%). LC-MS: M/Z744 (M+).
Device embodiments
1. First embodiment
The ITO glass substrate was patterned to have a light emitting region of 3mm×3 mm. The patterned ITO glass substrate was then washed, then the substrate was placed in a vacuum chamber, and the standard pressure was set at 1 x 10 -6 torr. Thereafter, m-MTDATA is vapor-deposited on the ITO substrate to form a film of a thicknessA Hole Injection Layer (HIL) on which an alpha-NPD is vapor deposited to a thickness ofA Hole Transport Layer (HTL) on which CBP+ compound 1-1 (dopant) (10 wt%) was vapor-deposited to a thickness ofIs formed by vapor deposition of BAlq in sequence to form a light-emitting layer (EML) of a thickness ofA hole blocking layer, and then Alq3 is evaporated on the hole blocking layer to form a film with the thickness ofIs vapor deposited with LiF to form the electron transport layer with the thickness ofIs formed by vacuum evaporation of Al on the electron injection layer to a thickness of(Second electrode of cathode), ITO/m-MTDATA/α-NPDCBP+ Compound 1-1 (10 wt.%)/BAlq/Alq3/LiFAl (1200) is used for manufacturing an organic light-emitting device with a structure.
2. Second embodiment
An organic electroluminescent device of the second embodiment was manufactured by the same method as the first embodiment described above, except that the light emitting layer dopant of the organic electroluminescent device was replaced with the compound 1-1 of the first embodiment by the compound 1-6.
3. Third embodiment
An organic electroluminescent device of the third embodiment was manufactured by the same method as the first embodiment described above, except that the light-emitting layer dopant of the organic electroluminescent device was replaced with the compound 1-1 of the first embodiment by the compound 1-81.
4. Fourth embodiment
An organic electroluminescent device of the fourth embodiment was manufactured by the same method as the above-described first embodiment, except that the light-emitting layer dopant of the organic electroluminescent device was replaced with the compound 1-1 of the first embodiment by the compound 1-261.
5. Fifth embodiment
An organic electroluminescent device of the fifth embodiment was manufactured by the same method as the above-described first embodiment, except that the light-emitting layer dopant of the organic electroluminescent device was replaced with the compound 1-283 of the first embodiment.
6. Sixth embodiment
An organic electroluminescent device of the sixth embodiment was manufactured by the same method as the above-described first embodiment, except that the light-emitting layer dopant of the organic electroluminescent device was replaced with the compound 1-1 of the first embodiment by the compound 1-288.
7. Seventh embodiment
An organic electroluminescent device of the seventh embodiment was manufactured by the same method as the above-described first embodiment, except that the light-emitting layer dopant of the organic electroluminescent device was replaced with the compound 1-1 of the first embodiment by the compound 1-315.
8. Eighth embodiment
An organic electroluminescent device of the eighth embodiment was manufactured by the same method as the above-described first embodiment, except that the light-emitting layer dopant of the organic electroluminescent device was replaced with the compound 1-1 of the first embodiment by the compound 2-14.
9. Ninth embodiment
An organic electroluminescent device of the ninth embodiment was manufactured by the same method as the above-described first embodiment, except that the light-emitting layer dopant of the organic electroluminescent device was replaced with the compound 1-1 of the first embodiment by the compound 2-21.
10. Tenth embodiment
An organic electroluminescent device of the tenth embodiment was manufactured by the same method as the above-described first embodiment, except that the light-emitting layer dopant of the organic electroluminescent device was replaced with the compound 1-1 of the first embodiment by the compound 2-50.
11. Eleventh embodiment
An organic electroluminescent device of the eleventh embodiment was manufactured by the same method as the above-described first embodiment, except that the light-emitting layer dopant of the organic electroluminescent device was replaced with the compound 1-1 of the first embodiment by the compound 2-66.
12. Twelfth embodiment
An organic electroluminescent device of the twelfth embodiment is manufactured by the same method as the first embodiment described above, except that the light-emitting layer dopant of the organic electroluminescent device is replaced with the compound 1-1 of the first embodiment by the compound 2-107.
13. Thirteenth embodiment
An organic electroluminescent device of the thirteenth embodiment was manufactured by the same method as the first embodiment described above, except that the light-emitting layer dopant of the organic electroluminescent device was replaced with the compound 1-1 of the first embodiment by the compound 2-171.
14. Fourteenth embodiment
An organic electroluminescent device of the fourteenth embodiment was manufactured by the same method as the above-described first embodiment, except that the light emitting layer dopant of the organic electroluminescent device was replaced with the compound 1-1 of the first embodiment by the compound 2-180.
Comparative example 1
An organic electroluminescent device of comparative example 1 was prepared in the same manner as in the first embodiment described above, except that the light-emitting layer dopant of the organic electroluminescent device was replaced with the compound Ref-1 of the first embodiment.
The organic electroluminescent device fabricated was tested for voltage and efficiency at 10mA/cm 2 current using standard methods known in the art. The data are shown in table 1.
TABLE 1 electronic luminescence characteristics table device of organic electroluminescent device
As can be seen from table 1, the application of the metal platinum complex of the present invention as a dopant of a light emitting layer in an organic electroluminescent device, compared with the comparative example, obtained better starting voltage, light emitting efficiency of the device and lifetime of the device were all significantly improved. The metal platinum complex has a certain application value.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A platinum (II) complex containing imidazole structural units, wherein the structure of the complex is shown in formula (I):
Wherein Ar 1 is hydrogen or phenyl;
ar 2—Ar3 is any of the following formulae:
Wherein R 1、R2、R3、R4 is each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C18 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkylthio, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C30 aryl;
R 5 is selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1-C18 alkyl, substituted or unsubstituted C6-C30 aryl;
all groups may be partially deuterated or fully deuterated and when a substituent is present, the substitution may be one or more times; the substituents are optionally selected from one or more of hydrogen, deuterium, F, C-C18 alkyl, C6-C30 aryl.
2. The complex of claim 1, wherein each R 1、R2、R3、R4 is independently selected from the group consisting of hydrogen, deuterium hydrogen, phenyl, biphenyl, C1-C18 alkyl, C3-C10 cycloalkyl, -F, cyano 、-CD3、-CD2H、-CDH2、-CF3、-CF2H、-CFH2、-OCH3、-OCDH2、-OCD2H、-OCD3、-SCH3、-SCDH2、-SCD2H, and-SCD 3.
3. The complex of claim 1, wherein R 1-R5 is each independently selected from the group represented by the following formulas, at least one hydrogen of which may be substituted with deuterium:
4. The complex of claim 1, wherein the metal platinum complex is selected from any one of the following chemical structures:
5. use of the metal platinum complex according to any one of claims 1 to 4 for the preparation of an organic electroluminescent device.
6. An organic electroluminescent device comprising a cathode layer, an anode layer and an organic functional layer, the organic functional layer comprising a light-emitting layer, characterized in that the metal platinum complex according to any one of claims 1 to 4 is contained as a dopant in the organic functional layer.
7. A formulation comprising the metal platinum complex of any one of claims 1-4 and at least one solvent.
8. An organic optoelectronic device, comprising:
a first electrode;
A second electrode facing the first electrode;
the luminescent material layer is clamped between the first electrode and the second electrode;
wherein the luminescent material layer comprises the metal platinum complex according to any one of claims 1 to 4.
9. The organic optoelectronic device according to claim 8, wherein the organic optoelectronic device comprises an organic photovoltaic device, an organic electroluminescent device, an organic solar cell, an electronic paper, an organic photoreceptor, an organic thin film transistor, or an organic memory device.
10. A display or lighting device comprising the organic electroluminescent device as claimed in claim 6.
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