CN112538097B - Metal organic complex, preparation method and application thereof - Google Patents
Metal organic complex, preparation method and application thereof Download PDFInfo
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- CN112538097B CN112538097B CN202011409972.8A CN202011409972A CN112538097B CN 112538097 B CN112538097 B CN 112538097B CN 202011409972 A CN202011409972 A CN 202011409972A CN 112538097 B CN112538097 B CN 112538097B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 47
- 239000002184 metal Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 13
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000010511 deprotection reaction Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 150000007529 inorganic bases Chemical class 0.000 claims description 7
- 150000002940 palladium Chemical class 0.000 claims description 7
- 150000003057 platinum Chemical class 0.000 claims description 7
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229960002429 proline Drugs 0.000 claims description 6
- 229930182821 L-proline Natural products 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 239000013522 chelant Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 35
- 239000007787 solid Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000012043 crude product Substances 0.000 description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 9
- 239000004926 polymethyl methacrylate Substances 0.000 description 9
- 238000000295 emission spectrum Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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 3
- 238000001035 drying Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001793 charged compounds Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- ROEQGIFOWRQYHD-UHFFFAOYSA-N (2-methoxyphenyl)boronic acid Chemical compound COC1=CC=CC=C1B(O)O ROEQGIFOWRQYHD-UHFFFAOYSA-N 0.000 description 1
- WZVWSOXTTOJQQQ-UHFFFAOYSA-N 2-bromo-6-(6-bromopyridin-2-yl)pyridine Chemical compound BrC1=CC=CC(C=2N=C(Br)C=CC=2)=N1 WZVWSOXTTOJQQQ-UHFFFAOYSA-N 0.000 description 1
- OYFFSPILVQLRQA-UHFFFAOYSA-N 3,6-ditert-butyl-9h-carbazole Chemical compound C1=C(C(C)(C)C)C=C2C3=CC(C(C)(C)C)=CC=C3NC2=C1 OYFFSPILVQLRQA-UHFFFAOYSA-N 0.000 description 1
- 229910020314 ClBr Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 239000010409 thin film Substances 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
- C07F15/0086—Platinum compounds
-
- 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
- C07F15/006—Palladium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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
-
- 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
- H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
-
- 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 invention relates to the technical field of photoelectric materials, in particular to a metal organic complex, a preparation method and application thereof. The metal organic complex has the following structural general formula:wherein M is selected from any one of Pt and Pd; r is R 1 ～R 9 Each independently selected from H, halogen, -OR a 、C 1～6 Any one of alkyl groups; r is R a Selected from H and C 1～6 Any one of alkyl groups. The invention provides a CNNO tetradentate chelate metal organic complex, which belongs to phosphorescent materials, and has excellent luminous efficiency, high electron mobility and long luminous life.
Description
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to a metal organic complex, a preparation method and application thereof.
Background
Organic light emitting diodes (Organic Light Emitting Diodes, OLEDs) are light emitting diodes using organic compounds as a light emitting layer material, and since the advent of the technology, have been widely focused on academia and industry because of their advantages such as self-luminescence, high light emitting efficiency, full color capability, wide viewing angle, high contrast, low power consumption, low weight, potentially large area color display, and flexibility, and have advantages such as simple manufacturing and low production cost. The phosphorescent organic light emitting diode (Phosphorescent Organic Light Emitting Diodes, abbreviated as pholes) has great development potential in the aspects of flat panel displays, lighting applications and the like because the internal theoretical luminous quantum efficiency of the phosphorescent organic light emitting diode (Phosphorescent Organic Light Emitting Diodes, abbreviated as pholes) is 100% by utilizing the single-state (25%) and the triplet (75%) to emit light at the same time.
Although various OLEDs products have been commercialized for many years, there is still a great need for efficient, stable, easy-to-process light emitting devices. Currently, OLEDs have some drawbacks that require improvement.
In view of this, the present invention has been made.
Disclosure of Invention
The first objective of the present invention is to provide a metal organic complex to solve the technical problems of low luminous efficiency in the prior art.
The second aim of the invention is to provide a preparation method of the metal organic complex, which is simple to operate and mild in condition.
A third object of the present invention is to provide the use of metal organic complexes in organic light emitting diodes.
A fourth object of the present invention is to provide an organic light emitting diode.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the metal organic complex has the following structural general formula:
wherein M is selected from any one of Pt and Pd;
R 1 ～R 9 each independently selected from H, halogen, -OR a And C 1～6 Any one of alkyl groups;
R a selected from H and C 1～6 Any one of alkyl groups.
In a specific embodiment of the invention, R 1 ～R 9 All are H.
The invention also provides a preparation method of the metal organic complex, which comprises the following steps:
the platinum salt or palladium salt and the compound I are subjected to reflux reaction in a solvent;
wherein the structural formula of the compound I is as follows:
in a specific embodiment of the present invention, the process for the preparation of compound i comprises the steps of:
deprotection reaction of compound II and boron tribromide in solvent;
wherein the structural formula of the compound II is as follows:
in a specific embodiment of the present invention, the process for preparing compound ii comprises the steps of:
carrying out Suzuki coupling reaction on the compound III and the compound IV in a solvent under the action of a catalyst;
wherein, the structural formulas of the compound III and the compound IV are respectively as follows:
x is selected from Cl, br or I.
In a specific embodiment of the present invention, the process for the preparation of compound III comprises the steps of:
the compound V reacts with the compound VI in a solvent under the action of L-proline/CuI and inorganic base;
wherein, the structural formulas of the compound V and the compound VI are respectively as follows:
y is selected from ClBr or I.
The invention also provides application of any metal-organic complex in the organic light-emitting diode.
The invention also provides an organic light-emitting diode, which comprises any one of the metal-organic complexes.
In a specific embodiment of the present invention, the organic light emitting diode comprises an emissive layer comprising any one of the above-described metal-organic complexes.
Compared with the prior art, the invention has the beneficial effects that:
(1) The metal organic complex has high luminous efficiency and high electron mobility;
(2) The metal organic complex can be used as a luminescent center for an emission layer of an organic light-emitting diode.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a metal-organic complex C according to example 1 of the present invention 1 Is a high resolution mass spectrum of (2); wherein (a) is a positive ion mode (2M+H) + ) Molecular ion peaks; (b) Is in positive ion mode (2M+H) + ) Theoretical simulation peaks;
FIG. 2 shows compound II of example 1 of the present invention 1 Nuclear magnetic hydrogen spectrogram of (2);
FIG. 3 is a metal organic complex C according to example 1 of the present invention 1 Nuclear magnetic hydrogen spectrogram of (2);
FIG. 4 is a metal organic complex C according to example 2 of the present invention 1 Is a high resolution mass spectrum of (2); wherein (a) is positive ion mode (M+H) + ) Molecular ion peaks; (b) In positive ion mode (M+H) + ) Theoretical simulation peaks;
FIG. 5 shows a metal-organic complex C according to example 1 of the present invention 1 Ultraviolet-visible absorption spectrum in solution state;
FIG. 6 is a metal-organic complex C according to example 2 of the present invention 2 Ultraviolet-visible absorption spectrum in solution state;
FIG. 7 shows a metal-organic complex C according to example 1 of the present invention 1 Emission spectrum in solid state;
FIG. 8 is a metal-organic complex C according to example 2 of the present invention 2 Emission spectrum in solid state;
FIG. 9 is a metal-organic complex C according to example 1 of the present invention 1 Emission spectrum in PMMA film state;
FIG. 10 is a metal-organic complex C according to example 2 of the present invention 2 Emission spectrum in PMMA film state;
FIG. 11 is a metal-organic complex C according to example 1 of the present invention 1 Emission spectrum in solution state;
FIG. 12 is a metal-organic complex C according to example 2 of the present invention 2 Emission spectrum in solution state;
FIG. 13 is a metal-organic complex C according to example 1 of the present invention 1 TGA analysis profile of (c);
FIG. 14 is a metal-organic complex C according to example 2 of the present invention 2 TGA analysis profile of (c).
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The metal organic complex has the following structural general formula:
wherein M is selected from any one of Pt and Pd;
R 1 ～R 9 each independently selected from H, halogen, -OR a And C 1～6 Any one of alkyl groups;
R a selected from H and C 1～6 Any one of alkyl groups.
The invention provides a CNNO tetradentate chelate metal organic complex, which belongs to phosphorescent materials, and has excellent luminous efficiency, high electron mobility and long luminous life.
In a specific embodiment of the invention, R 1 ～R 9 All are H.
Wherein C is 1～6 Alkyl refers to an alkyl group having 1 to 6 carbon atoms, and may be, for example, methyl, ethyl, propyl, isopropyl, and the like.
Specifically, the structural formula of the metal organic complex may be as follows:
the invention also provides a preparation method of the metal organic complex, which comprises the following steps:
the platinum salt or palladium salt and the compound I are subjected to reflux reaction in a solvent;
wherein the structural formula of the compound I is as follows:
in a specific embodiment of the invention, the platinum salt comprises potassium tetrachloroplatinate.
In a specific embodiment of the present invention, the palladium salt comprises palladium acetate.
In a specific embodiment of the present invention, the solvent comprises glacial acetic acid.
In a specific embodiment of the present invention, the molar ratio of the compound I to the platinum salt or palladium salt is 1: (0.8 to 1.2), preferably 1: (1 to 1.1), and may be 1:1, for example.
In a specific embodiment of the present invention, the ratio of compound I to solvent is 1 mmol/mL (300-500 mL), preferably 1 mmol/mL (320-450 mL).
In practice, the reflux reaction may be carried out at a temperature of 110 to 120℃for a period of 20 to 30 hours, preferably 22 to 26 hours, for example 24 hours.
In a specific embodiment of the invention, after the reflux reaction, the method further comprises cooling to room temperature, performing solid-liquid separation, collecting solid, washing the solid with glacial acetic acid, and drying to obtain a crude product. Further, the crude product is subjected to column chromatography separation to obtain the metal organic complex. Wherein, when column chromatography separation is carried out, dichloromethane and n-hexane can be used as eluent, and the volume ratio of the dichloromethane to the n-hexane is 1:1.
In a specific embodiment of the present invention, the process for the preparation of compound i comprises the steps of:
deprotection reaction of compound II and boron tribromide in solvent;
wherein the structural formula of the compound II is as follows:
in a specific embodiment of the present invention, the solvent in the deprotection reaction comprises methylene chloride. Further, the ratio of the compound II to the solvent may be 1 mmol/60 mL, for example, as 1 mmol/55 to 65 mL.
In a specific embodiment of the present invention, the molar ratio of the compound II to boron tribromide is 1:4 to 5, for example, 1:4 may be used.
In a specific embodiment of the invention, the temperature of the deprotection reaction is 55-65 ℃, and the time of the deprotection reaction is 10-18 h.
In a specific embodiment of the invention, after the deprotection reaction, cooling to room temperature, extracting the reacted material by using methylene dichloride, and collecting an organic phase; after the organic phase is dehydrated, the organic solvent is removed to obtain a crude product. Further, the crude product is subjected to column chromatography to obtain the compound I.
In a specific embodiment of the present invention, the process for preparing compound ii comprises the steps of:
carrying out Suzuki coupling reaction on the compound III and the compound IV in a solvent under the action of a catalyst; wherein, the structural formulas of the compound III and the compound IV are respectively as follows:
x is selected from Cl, br or I.
In a specific embodiment of the invention, the catalyst comprises tetra (triphenylphosphine) palladium and potassium carbonate, and the catalyst is used in a conventional amount in a Suzuki coupling reaction.
In a specific embodiment of the invention, the solvent for the Suzuki coupling reaction comprises water and tetrahydrofuran. Further, the volume ratio of water to tetrahydrofuran was 1:1. The ratio of the compound III to the solvent is 1 g/35-45 mL. For example, the concentration may be 1 g/40 mL.
In a specific embodiment of the invention, the temperature of the Suzuki coupling reaction is 75-85 ℃, and the time of the Suzuki coupling reaction is 20-28 h, such as 24h. Further, the Suzuki coupling reaction is carried out under the protection of nitrogen.
In a specific embodiment of the present invention, the molar ratio of the compound III to the compound IV is 1: (1 to 5), for example, 1: (4 to 5).
In a specific embodiment of the invention, after the Suzuki coupling reaction, cooling to room temperature, carrying out solid-liquid separation, collecting liquid, then removing solvent, and purifying by a column chromatography separation mode to obtain the compound II.
In a specific embodiment of the present invention, the process for the preparation of compound III comprises the steps of:
the compound V reacts with the compound VI in a solvent under the action of L-proline/CuI and inorganic base; wherein, the structural formulas of the compound V and the compound VI are respectively as follows:
y is selected from Cl, br or I.
In a specific embodiment of the present invention, the inorganic base comprises potassium carbonate.
In a specific embodiment of the invention, the solvent comprises DMSO. The ratio of the compound V to the solvent is 1 mmol/3-5 mL, for example, 1 mmol/4 mL.
In a specific embodiment of the invention, the temperature of the reaction is 135-145 ℃, and the time of the reaction is 20-28 hours, such as 24 hours. Further, the reaction is carried out under a nitrogen protection condition.
In a specific embodiment of the invention, after the reaction is completed, the mixture is cooled to room temperature, liquid is collected by solid-liquid separation, the solvent in the liquid is removed, and the mixture is purified by column chromatography separation to obtain the compound III.
In a specific embodiment of the present invention, the molar ratio of compound V to compound VI is 1: (0.8 to 1.2), preferably 1: (1 to 1.1), and may be 1:1, for example.
In a specific embodiment of the present invention, the molar ratio of the compound V, L-proline, cuI and inorganic base may be 1: (0.15 to 0.25): (0.05 to 0.15): (1.5 to 2.5), for example, 1:0.2:0.1:2.
Specifically, the synthetic route for preparing the metal organic complex from the compound V and the compound VI is as follows:
the invention also provides application of any metal-organic complex in the organic light-emitting diode.
The invention also provides an organic light-emitting diode, which comprises any one of the metal-organic complexes.
In a specific embodiment of the present invention, the organic light emitting diode comprises an emissive layer comprising any one of the above-described metal-organic complexes.
Example 1
This example provides a metal organic complex C 1 The structural formula is as follows:
metal organic complexes C 1 The synthetic route of (2) is as follows:
the preparation method comprises the following specific steps:
(i) 6,6 '-dibromo-2, 2' -bipyridine (3.14 g,10.0 mmol), 3, 6-di-tert-butylcarbazole (2.79 g,10.0 mmol), L-pro line (0.230 g,2.00 mmol), cuI (0.190 g,1.00 mmol), and K 2 CO 3 (2.76 g,20.0 mmol) was dissolved in anhydrous dimethyl sulfoxide (40.0 mL), and the resulting mixture was heated under reflux at 140℃for 24h under nitrogen. After the completion of the reaction, the mixture after the reaction was cooled to room temperature, the filtrate was collected by filtration, the solvent was removed, and the residue was purified by a silica gel column to give a purified compound III 1 。
(ii) By reacting compound III 1 (1.00 g,1.95 mmol), 2-methoxyphenylboronic acid (1.22 g,8.00 mmol), tetrakis (triphenylphosphine) palladium (0.231 g,0.200 mmol) and potassium carbonate (2.21 g,16.0 mmol) were dissolved in water (20.0 mL) and tetrahydrofuran (20.0 mL) and then the result wasThe mixture of (C) was heated under reflux at 80℃for 24h under nitrogen protection. After the reaction was completed, the mixture after the reaction was cooled to room temperature, the filtrate was collected by filtration, the solvent was removed, and the residue was purified by a silica gel column to give a white solid as compound II 1 。
(iii) By reacting compound II 1 (0.270 mg,0.5 mmol) and boron tribromide (0.501 g,2.0 mmol) were dissolved in anhydrous dichloromethane (30.0 mL), and the mixed solution obtained by mixing was stirred at 60℃for 18h. After the reaction is finished, the reaction system is cooled to room temperature, dichloromethane is used for extraction, anhydrous magnesium sulfate is added into the collected organic phase for water removal, the magnesium sulfate is removed by filtration, the dichloromethane is removed by rotary evaporation, the crude product is obtained, and the white solid obtained after the purification of the crude product by a silica gel column is the compound I 1 。
(iv) By reacting compound I 1 (0.130 g,0.247 mmol) and potassium tetrachloroplatinate (0.103 g,0.247 mmol) were dissolved in glacial acetic acid (80.0 mL) and the resulting mixture was reacted at 115℃under reflux for 24h. After the reaction is finished, cooling to room temperature, filtering, washing the solid with glacial acetic acid, drying to obtain a crude product, purifying the crude product by a silica gel column to obtain an orange solid which is a metal organic complex C 1 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the eluent is dichloromethane and n-hexane with the volume ratio of 1:1.
Example 2
This example provides a metal organic complex C 2 The structural formula is as follows:
metal organic complexes C 2 The synthetic route of (2) is as follows:
specific preparation steps reference example 1, except that step (iv) was replaced with step (v), which is specifically as follows:
(v) Will be combinedArticle I 1 (0.0936 g,0.178 mmol) and palladium acetate (0.0400 g,0.178 mmol) were dissolved in glacial acetic acid (80.0 mL) and the resulting mixture was reacted at 115℃under reflux for 24h. After the reaction is finished, cooling to room temperature, filtering, washing the solid with glacial acetic acid, drying to obtain a crude product, purifying the crude product by a silica gel column to obtain a yellow solid which is a metal organic complex C 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the eluent is dichloromethane and n-hexane with the volume ratio of 1:1.
Experimental example 1
The metal organic complex C synthesized by the invention 1 And metal organic complexes C 2 The structural characterization data of (2) are as follows:
FIG. 1 is a metal-organic complex C according to example 1 of the present invention 1 FIG. 2 is a high resolution spectrum of Compound II of example 1 of the present invention 1 Is shown in FIG. 3, which is a metal organic complex C of example 1 of the present invention 1 FIG. 4 shows the nuclear magnetic resonance spectrum of the metal organic complex C of example 2 of the present invention 1 Is a high resolution mass spectrum of (c). The structural characterization data prove that the metal organic complex C is successfully prepared 1 And metal organic complexes C 2 。
Experimental example 2
FIGS. 5 and 6 are, respectively, metal-organic complexes C prepared according to the invention 1 And metal organic complexes C 2 In the state of solution (metal-organic complex C 1 And metal organic complexes C 2 Respectively dissolved in methylene chloride) at 25 ℃.
FIGS. 7 and 8 show the metal-organic complex C prepared according to the present invention 1 And metal organic complexes C 2 The phosphorescence emission spectrum at 25 ℃ in the solid state has excitation wavelengths of 520nm and 473nm respectively.
FIGS. 9 and 10 show the metal-organic complex C prepared according to the present invention 1 And metal organic complexes C 2 The phosphorescence emission spectrum at 25 ℃ in the PMMA film state has excitation wavelengths of 520nm and 473nm respectively. Wherein, the metal organic complex in the PMMA film is addedThe addition amount is 2wt% and the rest is PMMA (PMMA film is prepared by conventional method, for example, metal organic complex sample and polymethyl methacrylate are dissolved in dichloromethane (ACS grade) according to mass ratio of 1:49, and the solution is dripped on the surface of quartz glass, and the solvent is volatilized.
FIGS. 11 and 12 show the metal-organic complex C prepared according to the present invention 1 And metal organic complexes C 2 In the state of solution (metal-organic complex C 1 And metal organic complexes C 2 Respectively dissolved in methylene chloride) at 25 deg.c, the excitation wavelengths are 520nm and 473nm, respectively.
The emission maps of fig. 7 to 12 are normalized results, so that comparison is convenient. The specific normalization method is a conventional normalization method, such as: the spectral data is divided by the highest peak at the same time, so that the highest peak becomes 1.
FIGS. 13 and 14 are respectively a metal-organic complex C prepared according to the present invention 1 And metal organic complexes C 2 TGA profile under nitrogen (heating rate 34.4 ℃/min).
For the metal organic complex C prepared by the invention 1 And metal organic complexes C 2 The luminescence properties under the above different conditions are summarized in Table 1.
TABLE 1 luminescence properties of different metal-organic complexes in different states
Remarks: in the tables, "Em" represents "emission wavelength", "Φ" represents "phosphorescence quantum yield", "τ" represents "phosphorescence lifetime", "Solid" represents "Solid state", "PMMA" represents "PMMA thin film state", and "Liquid" represents "solution state".
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (20)
1. The metal organic complex is characterized by having the following structural general formula:
；
wherein M is selected from any one of Pt and Pd;
R 1 ~R 9 each independently selected from H and C 1~6 Any one of alkyl groups;
R a selected from H and C 1~6 Any one of alkyl groups.
2. The metal-organic complex according to claim 1, wherein R 1 ~R 9 All are H.
3. The method for producing a metal-organic complex according to claim 1 or 2, characterized by comprising the steps of:
the platinum salt or palladium salt and the compound I are subjected to reflux reaction in a solvent;
wherein the structural formula of the compound I is as follows:
。
4. a method of preparing a metal organic complex according to claim 3, wherein the platinum salt comprises potassium tetrachloroplatinate and the palladium salt comprises palladium acetate.
5. A method of preparing a metal organic complex according to claim 3, wherein the solvent comprises glacial acetic acid.
6. The method for producing a metal-organic complex according to claim 3, wherein the molar ratio of the platinum salt or palladium salt to the compound I is (0.8 to 1.2):1.
7. A process for the preparation of a metal-organic complex according to claim 3, characterized in that the process for the preparation of compound i comprises the steps of:
deprotection reaction of compound II and boron tribromide in solvent;
wherein the structural formula of the compound II is as follows:
。
8. the method for preparing a metal-organic complex according to claim 7, wherein the temperature of the deprotection reaction is 55-65 ℃, and the time of the deprotection reaction is 10-18 hours.
9. The method for producing a metal-organic complex according to claim 7, wherein the molar ratio of the compound II to boron tribromide is 1: (4-5).
10. The method for preparing a metal-organic complex according to claim 7, wherein the method for preparing the compound ii comprises the steps of:
carrying out Suzuki coupling reaction on the compound III and the compound IV in a solvent under the action of a catalyst; wherein, the structural formulas of the compound III and the compound IV are respectively as follows:
、/>the method comprises the steps of carrying out a first treatment on the surface of the X is selected from Cl, br or I.
11. The preparation method of the metal-organic complex according to claim 10, wherein the temperature of the Suzuki coupling reaction is 75-85 ℃, and the time of the Suzuki coupling reaction is 20-28 h.
12. The method for producing a metal-organic complex according to claim 10, wherein the molar ratio of the compound iii to the compound iv is 1:1-5.
13. The process for preparing a metal-organic complex according to claim 10, wherein the process for preparing the compound iii comprises the steps of:
the compound V reacts with the compound VI in a solvent under the action of L-proline/CuI and inorganic base; wherein, the structural formulas of the compound V and the compound VI are respectively as follows:
、/>the method comprises the steps of carrying out a first treatment on the surface of the Y is selected from Cl, br or I.
14. The method for preparing a metal-organic complex according to claim 13, wherein the inorganic base comprises potassium carbonate.
15. The method for preparing a metal-organic complex according to claim 13, wherein the reaction temperature is 135-145 ℃ and the reaction time is 20-28 h.
16. The method for producing a metal-organic complex according to claim 13, wherein the molar ratio of the compound v to the compound vi is 1: (0.8 to 1.2).
17. The method according to claim 13, wherein the molar ratio of the compound v, L-proline, cuI and inorganic base is 1:0.15 to 0.25:0.05 to 0.15:1.5 to 2.5.
18. Use of the metal-organic complex according to claim 1 or 2 in an organic light emitting diode.
19. An organic light-emitting diode comprising the metal-organic complex according to claim 1 or 2.
20. The organic light-emitting diode of claim 19, wherein the organic light-emitting diode comprises an emissive layer, the metal-organic complex disposed in the emissive layer.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4769292A (en) * | 1987-03-02 | 1988-09-06 | Eastman Kodak Company | Electroluminescent device with modified thin film luminescent zone |
| US5061569A (en) * | 1990-07-26 | 1991-10-29 | Eastman Kodak Company | Electroluminescent device with organic electroluminescent medium |
| US5247190A (en) * | 1989-04-20 | 1993-09-21 | Cambridge Research And Innovation Limited | Electroluminescent devices |
| US5703436A (en) * | 1994-12-13 | 1997-12-30 | The Trustees Of Princeton University | Transparent contacts for organic devices |
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| KR20180137311A (en) * | 2017-06-16 | 2018-12-27 | 삼성전자주식회사 | Organometallic compound, organic light emitting device including the same and a composition for diagnosing including the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4769292A (en) * | 1987-03-02 | 1988-09-06 | Eastman Kodak Company | Electroluminescent device with modified thin film luminescent zone |
| US5247190A (en) * | 1989-04-20 | 1993-09-21 | Cambridge Research And Innovation Limited | Electroluminescent devices |
| US5061569A (en) * | 1990-07-26 | 1991-10-29 | Eastman Kodak Company | Electroluminescent device with organic electroluminescent medium |
| US5703436A (en) * | 1994-12-13 | 1997-12-30 | The Trustees Of Princeton University | Transparent contacts for organic devices |
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