CN111690016A - Iridium coordination compound, preparation method thereof and photoelectric device - Google Patents
Iridium coordination compound, preparation method thereof and photoelectric device Download PDFInfo
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- CN111690016A CN111690016A CN202010663881.0A CN202010663881A CN111690016A CN 111690016 A CN111690016 A CN 111690016A CN 202010663881 A CN202010663881 A CN 202010663881A CN 111690016 A CN111690016 A CN 111690016A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 108
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 84
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052757 nitrogen Chemical group 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000003446 ligand Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 229910052710 silicon Chemical group 0.000 claims abstract description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims abstract description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 3
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 239000010703 silicon Chemical group 0.000 claims abstract description 3
- 239000010410 layer Substances 0.000 claims description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012044 organic layer Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 4
- 230000005693 optoelectronics Effects 0.000 claims description 4
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 4
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-N 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000005303 weighing Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000001819 mass spectrum Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 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
- KDOQMLIRFUVJNT-UHFFFAOYSA-N 4-n-naphthalen-2-yl-1-n,1-n-bis[4-(n-naphthalen-2-ylanilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC=CC=C1N(C=1C=C2C=CC=CC2=CC=1)C1=CC=C(N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C=CC=CC3=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C=CC=CC3=CC=2)C=C1 KDOQMLIRFUVJNT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
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- 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
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
- C07B59/002—Heterocyclic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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- 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
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/05—Isotopically modified compounds, e.g. labelled
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- 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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- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses an iridium coordination compound, a preparation method thereof and a photoelectric device, belonging to the field of chemical synthesis and photoelectric materials, and the iridium coordination compound has a structural general formula as follows:
wherein X is carbon or silicon; y is carbon or nitrogen; m and n are integers not less than 1, and m + n is 3; r1、R2、R3、R4、R5、R6、R7Independently of hydrogen, deuterium, halogen, cyano, alkyl, aryl and heteroarylAt least one of them. The iridium coordination compound provided by the embodiment of the invention is combined by selecting a specific heterocyclic ligand so as to adjust the wavelength of the coordination compound; when the iridium coordination compound is used for photoelectric devices such as organic electroluminescent devices and the like, the luminous efficiency and the brightness of the photoelectric devices can be improved.
Description
Technical Field
The invention relates to the field of chemical synthesis and photoelectric materials, in particular to an iridium coordination compound, a preparation method thereof and a photoelectric device.
Background
Organic light emitting diodes are also called organic electroluminescent displays, organic light emitting semiconductors. The OLED display technology has the advantages of self-luminescence, wide viewing angle, almost infinite contrast, low power consumption, extremely high reaction speed and the like. The organic electroluminescence technology is a latest generation flat panel display technology, and can be used for flat panel displays and illumination light sources, and currently, commercial flat panel displays are put into the market, and the illumination light sources are rapidly industrialized due to their own absolute advantages. The electroluminescent device has an all-solid-state structure, organic electroluminescent materials are the core and the foundation of the device, and the development of new materials is the source power for promoting the continuous progress of the electroluminescent technology. The preparation of the original material and the optimization of the device are also the research hotspots of the organic electroluminescent industry at present.
The phosphorescence luminescent phenomenon is always favored since the discovery, because the luminescent efficiency of the phosphorescence material is obviously higher than the luminescent efficiency of the fluorescence, theoretically reaching 100 percent of the luminescent efficiency, many scientific research institutions are increasing the research and development of the phosphorescence material and trying to accelerate the industrialized development through the phosphorescence material; however, the phosphor material has high synthesis cost, high synthesis process requirements, high purification requirements and low efficiency, and easily pollutes the environment in the synthesis process.
Disclosure of Invention
An object of an embodiment of the present invention is to provide an iridium complex compound to solve the problems set forth in the background art.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
an iridium complex compound having a general structural formula of formula L:
wherein X is carbon or silicon; y is carbon or nitrogen;
m and n are integers not less than 1, and m + n is 3;
R1、R2、R3、R4、R5、R6、R7independently at least one of hydrogen, deuterium, halogen, cyano, alkyl, aryl and heteroaryl.
Preferably, the structural general formula of the iridium complex compound is shown as formula L-I or formula L-II:
preferably, said R is1、R2、R5、R6And R7The substitution positions of (a) are respectively arbitrary positions of the ring in which they are present.
Preferably, said R is1、R2And R7The number of substituents each independently comprises is 0 to 4; the R is5The number of the substituents is 0 to 3; the R is3The number of the substituents is 0 to 2.
Preferably, the alkyl is C1-C6 straight-chain alkyl, branched-chain alkyl and cycloalkyl; the aryl is C6-C12 aryl; the aromatic heterocyclic group is an aromatic heterocyclic group having C3-C12.
Preferably, the iridium complex compound has a chemical structural formula of any one of formula L001 to formula L093:
another object of an embodiment of the present invention is to provide a method for preparing the iridium complex compound, wherein the method for preparing the iridium complex compound with a general structural formula of L-I includes the following steps:
reacting a compound A1 with a general formula of A-01 with iridium trichloride to obtain a bridging ligand B1 with a general formula of B-01;
reacting the bridging ligand B1 with silver trifluoromethanesulfonate and methanol to obtain an intermediate C1 with a general formula of C-01;
reacting the intermediate C1 with a compound D1 with a general formula D-01 to obtain the iridium coordination compound;
the preparation method of the iridium coordination compound with the structural general formula of L-II comprises the following steps:
reacting a compound A2 with a general formula of A-02 with iridium trichloride to obtain a bridging ligand B2 with a general formula of B-02;
reacting the bridging ligand B2 with silver trifluoromethanesulfonate and methanol to obtain an intermediate C2 with a general formula of C-02;
reacting the intermediate C2 with a compound D2 with a general formula D-02 to obtain the iridium coordination compound;
specifically, the synthesis route of the iridium complex compound with the structural general formula of L-I is as follows:
the synthesis route of the iridium coordination compound with the structural general formula of L-II is as follows:
another object of an embodiment of the present invention is to provide an application of the iridium complex compound in preparation of an organic electroluminescent device.
It is another object of an embodiment of the present invention to provide an optoelectronic device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, the organic layer comprising the iridium complex compound described above.
Preferably, the organic layer includes a light emitting layer; the light-emitting layer includes a host material and the iridium complex compound.
Preferably, the host material is 4,4'-N, N' -biphenyl dicarbazole.
The photoelectric device may be an organic electroluminescent device, an organic solar cell, electronic paper, an organic photoreceptor, an organic thin film transistor, or the like, but is not limited thereto; the organic layer may further include at least one layer of a hole injection layer, a hole transport layer, a composite layer of hole injection and hole transport technical layers, an electron blocking layer, a hole blocking layer, an electron transport layer, an electron injection layer, an electron transport layer, and a composite layer of electron injection technical layers, and at least one layer thereof may or may not include the iridium complex compound described above, but is not limited thereto.
In addition, the host material can be selected from other types of organic compounds, and is not limited to 4,4'-N, N' -biphenyl dicarbazole;
preferably, the mass ratio of the host material to the iridium complex compound is (90-99.5): (0.5-10).
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
according to the iridium coordination compound provided by the embodiment of the invention, the wavelength of the coordination compound is adjusted by selecting the combination of specific heterocyclic ligands; when the iridium coordination compound is used for photoelectric devices such as organic electroluminescent devices and the like, the luminous efficiency and the brightness of the photoelectric devices can be improved. In addition, the preparation method of the iridium coordination compound provided by the embodiment of the invention has simple preparation steps and high product purity.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Compound example 1
The embodiment of the compound provides an iridium coordination compound, the chemical structural formula of which is formula L001 in the summary of the invention, and the reaction route of the preparation method of the iridium coordination compound is as follows:
the specific preparation method comprises the following steps:
(1) weighing compound A-001 (64.5 mmol, 10g of 2-phenylpyridine) and IrCl under the protection of nitrogen3·3H2O (24.8mmo1, 8.75g) is put into a reaction system, a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of purified water is added, reflux is carried out for 24 hours at 120 ℃ under the protection of nitrogen, then cooling is carried out to 25 ℃, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. This gave bridging ligand B-001(6.64g, 50% yield) as a yellow powder.
(2) The bridging ligand B-001(4.67mmol, 5g) was weighed, silver trifluoromethanesulfonate (14mmol, 3.6g) was added, 100mL of dichloromethane was added to the system, 40mL of methanol was added, stirring was performed at 25 ℃ for 24 hours under nitrogen protection, the reaction solution was distilled until no liquid flowed out, and the filtrate of column chromatography (short column) was concentrated until solid precipitated to give intermediate C-001(6.2g, 93%) as a yellow powder.
(3) Weighing intermediate C-001(8.7mmol, 6.2g), adding compound D-001(26.1mmol, 7.5g), adding anhydrous ethanol 180mL into the system, refluxing at 90 deg.C for 24 hr under nitrogen protection, filtering, washing with alcohol, and oven drying; then, methylene chloride was used as a solvent, and silica gel column chromatography was performed to concentrate the filtrate to precipitate a solid, whereby the final yellow iridium complex compound L001(2g, yield 29.2%) was obtained.
The above iridium complex compound L001 was subjected to the following analytical test:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 787.20; the test value was 787.21.
Elemental analysis: calculated value C62.57%; 4.10 percent of H; 5.34 percent of N; 24.42 percent of Ir; 3.57 percent of Si. The test value C is 62.60%; 4.12 percent of H; 5.35 percent of N; 24.40 percent of Ir; 3.60 percent of Si.
Compound example 2
The embodiment of the compound provides an iridium coordination compound, the chemical structural formula of which is shown as formula L019 in the invention content, and the reaction route of the preparation method of the iridium coordination compound is as follows:
the specific preparation method comprises the following steps:
(1) weighing compound A-019(58mmol, 10g) and IrCl under the protection of nitrogen3·3H2O (19.3mmo1, 6.8g) is put into a reaction system, a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of purified water is added, reflux is carried out for 24 hours at 120 ℃ under the protection of nitrogen, then cooling is carried out to 25 ℃, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. Bridging ligand B-019 was obtained as a yellow powder (6.6g, 60% yield).
(2) Weighing bridging ligand B-019(5.8mmol, 6.6g), adding silver trifluoromethanesulfonate (17.4mmol, 4.5g), adding 130mL of dichloromethane into the system, adding 50mL of methanol, stirring for 24 hours at 25 ℃ under the protection of nitrogen, distilling the reaction solution until no liquid flows out, and concentrating the filtrate of column chromatography (short column) until solid is separated out to obtain intermediate C-019(7.8g, yield 90%) of yellow green powder.
(3) Weighing intermediate C-019(8.24mmol, 8.1g), adding compound D-019(24.72mmol, 7.74g), adding 250mL of absolute ethanol into the system, refluxing at 90 ℃ for 24 hours under the protection of nitrogen, filtering, washing with alcohol, and drying; then, methylene chloride was used as a solvent, and the filtrate was subjected to silica gel column chromatography to concentrate a solid to precipitate, thereby obtaining a final yellow iridium complex compound L019(2.6g, yield 35.1%).
The above iridium complex compound L019 was subjected to the following analytical test:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 899.29; the test value was 899.30.
Elemental analysis: calculated value C60.11%; 4.93 percent of H; f: 4.23 percent; 6.23 percent of N; 21.38 percent of Ir; si: 3.12 percent. 60.11% of test value C; 4.93 percent of H; f: 4.23 percent; 6.23 percent of N; 21.38 percent of Ir; si: 3.12 percent.
Compound example 3
The embodiment of the compound provides an iridium coordination compound, the chemical structural formula of which is shown as formula L054 in the summary of the invention, and the reaction route of the preparation method of the iridium coordination compound is as follows:
the specific preparation method comprises the following steps:
(1) weighing compound A-054(70.9mmol, 20g) and IrCl under nitrogen protection system3·3H2O (23.6mmo1, 8.3g) is put into a reaction system, a mixed solution of 600mL of ethylene glycol ethyl ether and 200mL of purified water is added, reflux is carried out for 18 hours at 120 ℃ under the protection of nitrogen, then cooling is carried out to 25 ℃, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. The bridged ligand B-054(9.3g, 50% yield) was obtained as a yellow powder.
(2) Weighing bridging ligand B-054(5.9mmol, 9.3g), adding silver trifluoromethanesulfonate (17.7mmol, 4.55g), adding dichloromethane 200mL, adding methanol 50mL, stirring at 25 ℃ for 24 hours under the protection of nitrogen, distilling the reaction liquid until no liquid flows out, and concentrating the filtrate of column chromatography (short column) until solid is separated out to obtain intermediate C-054(10.3g, yield 90%) as yellow green powder.
(3) Weighing intermediate C-054(10.7mmol, 10.3g), adding compound D-054(32.1mmol, 9.3g), adding anhydrous ethanol 300mL into the system, refluxing at 90 deg.C for 12 hr under nitrogen protection, filtering, washing with alcohol, and oven drying; then, methylene chloride was used as a solvent, and the filtrate was subjected to silica gel column chromatography to concentrate a solid to precipitate, thereby obtaining a final yellow iridium complex compound L054(3g, yield 26.8%).
The above iridium complex compound L054 was subjected to the following analytical test:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 1043.52; the test value was 1043.50.
Elemental analysis: calculated value C69.06%; 7.14 percent of H; 5.37 percent of N; 18.42 percent of Ir. 69.10% of test value C; 7.18 percent of H; 5.40 percent of N; 18.40 percent of Ir.
Compound example 4
The embodiment of the compound provides an iridium coordination compound, the chemical structural formula of which is formula L074 in the summary of the invention, and the reaction route of the preparation method of the iridium coordination compound is as follows:
the specific preparation method comprises the following steps:
(1) weighing compound A-074(35.7mmol, 10g) and IrCl under nitrogen protection system3·3H2Adding O (11.9mmo1, 4.2g) into a reaction system, adding a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of purified water, refluxing for 18 hours at 120 ℃ under the protection of nitrogen, cooling to 25 ℃, precipitating, filtering the precipitate, and washing and drying with water, absolute ethyl alcohol and petroleum ether in sequence. Bridged ligand B-074(5g, 53% yield) was obtained as a yellow powder.
(2) Weighing bridging ligand B-074(3.2mmol, 5g), adding silver trifluoromethanesulfonate (9.6mmol, 2.5g), adding 100mL of dichloromethane, 25mL of methanol, stirring at 25 ℃ for 24 hours under the protection of nitrogen, distilling the reaction solution until no liquid flows out, and concentrating the filtrate of column chromatography (short column) until solid is separated out to obtain intermediate C-074(4.02g, 92% yield) as yellow-green powder.
(3) Weighing intermediate C-074(5.9mmol, 4.02g), adding compound D-074(17.7mmol, 3.2g), adding 300mL of absolute ethanol into the system, refluxing at 120 ℃ for 12 hours under the protection of nitrogen, filtering, washing with alcohol, and drying; then, methylene chloride was used as a solvent, and silica gel column chromatography was performed to concentrate the filtrate to precipitate a solid, thereby obtaining a final yellow iridium complex compound L074(1.65g, yield 30%).
The above iridium complex compound L074 was subjected to the following analytical test:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 930.37; the test value was 930.4.
Elemental analysis: calculated value C64.56%; 5.74 percent of H; 9.03 percent of N; 20.66 percent of Ir. 64.60% of test value C; 5.70 percent of H; 9.00 percent of N; 20.70 percent of Ir.
Compound example 5
The embodiment of the compound provides an iridium coordination compound, the chemical structural formula of which is shown as formula L086 in the summary of the invention, and the reaction route of the preparation method of the iridium coordination compound is as follows:
the specific preparation method comprises the following steps:
(1) weighing compound A-086(58mmol, 10g) and IrCl under the protection of nitrogen3·3H2O (19.3mmo1, 6.8g) is put into a reaction system, a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of purified water is added, reflux is carried out for 24 hours at 120 ℃ under the protection of nitrogen, then cooling is carried out to 25 ℃, precipitates are separated out, the precipitates are filtered by suction, and water, absolute ethyl alcohol and petroleum ether are used for washing and drying in sequence. Bridged ligand B-086(6.6g, 60% yield) was obtained as a yellow powder.
(2) The bridging ligand B-086(5.8mmol, 6.6g) was weighed, silver trifluoromethanesulfonate (17.4mmol, 4.5g) was added, 130mL of dichloromethane was added to the system, 50mL of methanol was added, stirring was carried out at 25 ℃ for 24 hours under nitrogen protection, the reaction solution was distilled until no liquid flowed out, and the filtrate of column chromatography (short column) was concentrated until solid was precipitated, yielding intermediate C-086(7.8g, 90% yield) as a yellow powder.
(3) Weighing intermediate C-086(10.5mmol, 7.8g), adding compound D-086(31.5 mmol, 8.5g), adding 250mL of absolute ethanol into the system, refluxing at 90 ℃ for 12 hours under the protection of nitrogen, filtering, washing with alcohol, and drying; then, methylene chloride was used as a solvent, and silica gel column chromatography was performed to concentrate the filtrate to precipitate a solid, thereby obtaining a final yellow iridium complex compound L086(2.6g, yield 30.6%).
The above iridium complex compound L086 was subjected to the following analytical test:
HPLC purity: greater than 99%.
Mass spectrum: calculated value 805.29; the test value was 805.30.
Elemental analysis: the calculated value C is 65.65 percent; 5.26 percent of H; 5.22 percent of N; 23.88 percent of Ir; the test value is 65.65 percent; 5.30 percent of H; 5.20 percent of N; 23.90 percent of Ir.
The synthetic routes and principles of the preparation methods of other iridium coordination compounds with the structural general formula of formula L in the summary of the invention are the same as those of the compounds in the embodiments 1 to 5 listed above, so that the invention is not exhaustive, and a plurality of iridium coordination compounds are selected as the compounds in the embodiments 6 to 13, specifically as follows.
Examples 6 to 13 of the Compounds
According to the preparation method of the compound examples 1 to 5, the raw materials are respectively replaced by compounds corresponding to corresponding ligand structures in the target product, so that a series of iridium coordination compounds are obtained, and the following table 1 is shown.
TABLE 1
The embodiment of the invention also provides a photoelectric device prepared by using the iridium coordination compound provided by the embodiment, and particularly, the photoelectric device is an organic electroluminescent device, wherein the organic electroluminescent device comprises a first electrode, a second electrode and at least one organic layer arranged between the first electrode and the second electrode.
The organic layer may include at least one layer selected from a hole injection layer, a hole transport layer, a composite layer of hole injection and hole transport technical layers, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, an electron transport layer, and a composite layer of electron injection technical layers, and at least one layer may or may not include the iridium complex compound.
Specifically, the light-emitting layer includes a host material and the iridium complex compound; wherein, the main material can be 4,4'-N, N' -biphenyl dicarbazole; the mass ratio of the host material to the iridium complex compound can be controlled to be (90-99.5): 0.5-10.
In practical applications, the method for manufacturing the organic electroluminescent device can refer to device example 1 below.
Device example 1
The device embodiment 1 provides a method for manufacturing an organic electroluminescent device, which includes the steps of:
s1, coating the coating with the thickness of
The ITO glass substrate is put in distilled water for cleaning for 2 times, ultrasonic cleaning is carried out for 30 minutes, the ITO glass substrate is repeatedly cleaned for 2 times by distilled water and is ultrasonically cleaned for 10 minutes, after the cleaning by distilled water is finished, the ITO glass substrate is sequentially ultrasonically cleaned by solvents such as isopropanol, acetone, methanol and the like (once each time, each time is cleaned for 10 minutes), then is dried, is transferred into a plasma cleaning machine for cleaning for 5 minutes, and then is sent into an evaporation machine for evaporation according to the following steps:
s2, firstly, on an ITO glass substrate (anode), N1- (2-naphthyl) -N4, N4-di (4- (2-naphthyl (phenyl) amino) phenyl) -N1-phenyl benzene-1, 4-diamine ("2-TNATA")60 nm; next, N '-diphenyl-N, N' -di (1-naphthyl) -1, 1 '-biphenyl-4, 4' -diamine (NPB, 60nm) was evaporated as a Hole Transport Layer (HTL); then, a 30nm thick host material 4,4'-N, N' -biphenyldicarbazole ("CBP") and the iridium complex compound (dopant material) having a structural formula of L001 provided in the above compound example 1 were mixed-evaporated as a light-emitting layer on the hole transport layer at a mass ratio of 90: 10; and then, sequentially evaporating a hole blocking layer (BALq) with the thickness of 10nm, evaporating tris (8-hydroxyquinoline) aluminum (Alq3, 40nm) as an electron transport layer, LiF (0.2nm) as an electron injection layer and Al (150nm) as a cathode on the light-emitting layer, thus obtaining the organic electroluminescent device.
Device examples 2 to 13
Device examples 2 to 13 were prepared by referring to the preparation methods provided in device example 1 above, except that the iridium complex compound L001 in device example 1 above was replaced with iridium complex compounds L019, L054, L074, L086, L006, L012, L026, L033, L041, L062, L069, and L076, respectively.
Comparative device example 1
The comparative device example provides an organic electroluminescent device, and the only difference between the preparation method of the organic electroluminescent device and the device example 1 is that the organic electroluminescent device adopts Ir (ppy)3And (3) replacing the iridium coordination compound with the chemical structural formula of L001 as a doping material and carrying out mixed evaporation on the doping material and the main material CBP according to the mass ratio of 10: 90. Wherein, Ir (ppy)3The structural formula of (A) is:
experimental example:
the organic electroluminescent devices obtained in the device examples 1 to 13 and the device comparative example 1 were respectively subjected to a light emission characteristic test to evaluate the properties of the organic electroluminescent devices, such as driving voltage, light emission efficiency, and service life (T95), and specific test results are shown in table 2 below.
TABLE 2
As can be seen from Table 2 above, in contrast to the use of conventional Ir (ppy)3Compared with the organic electroluminescent device prepared by using the doping material of the luminescent layer, the iridium coordination provided by the embodiment of the inventionThe organic electroluminescent device prepared by using the compound as a luminescent layer doping material has the advantages of obviously reduced driving voltage, obviously improved luminous efficiency and obviously prolonged service life.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. An iridium complex compound, wherein the structural general formula of the iridium complex compound is formula L:
wherein X is carbon or silicon; y is carbon or nitrogen;
m and n are integers not less than 1, and m + n is 3;
R1、R2、R3、R4、R5、R6、R7independently at least one of hydrogen, deuterium, halogen, cyano, alkyl, aryl and heteroaryl.
2. The iridium complex compound according to claim 1, wherein the general structural formula of the iridium complex compound is formula L-I or formula L-II:
3. the iridium complex compound according to claim 2, wherein R is1、R2、R5、R6And R7The substitution positions of (a) are respectively arbitrary positions of the ring in which they are present.
4. The iridium complex compound according to claim 3, wherein R is1、R2And R7The number of substituents each independently comprises is 0 to 4; the R is5The number of the substituents is 0 to 3; the R is3The number of the substituents is 0 to 2.
5. The iridium complex compound according to claim 2, wherein the alkyl group is a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group having from C1 to C6; the aryl is C6-C12 aryl; the aromatic heterocyclic group is an aromatic heterocyclic group having C3-C12.
6. The iridium complex compound according to claim 2, wherein the chemical structural formula of the iridium complex compound is any one of the formulae L001 to L093:
7. a method for preparing an iridium complex compound as claimed in any one of claims 2 to 6, wherein the method for preparing an iridium complex compound having a general structural formula of formula L-I comprises the steps of:
reacting a compound A1 with a general formula of A-01 with iridium trichloride to obtain a bridging ligand B1 with a general formula of B-01;
reacting the bridging ligand B1 with silver trifluoromethanesulfonate and methanol to obtain an intermediate C1 with a general formula of C-01;
reacting the intermediate C1 with a compound D1 with a general formula D-01 to obtain the iridium coordination compound;
the preparation method of the iridium coordination compound with the structural general formula of L-II comprises the following steps:
reacting a compound A2 with a general formula of A-02 with iridium trichloride to obtain a bridging ligand B2 with a general formula of B-02;
reacting the bridging ligand B2 with silver trifluoromethanesulfonate and methanol to obtain an intermediate C2 with a general formula of C-02;
reacting the intermediate C2 with a compound D2 with a general formula D-02 to obtain the iridium coordination compound;
8. an optoelectronic device comprising a first electrode, a second electrode and at least one organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises an iridium complex compound as claimed in any one of claims 1 to 6.
9. The optoelectronic device according to claim 8, wherein the organic layer comprises a light-emitting layer; the light-emitting layer includes a host material and the iridium complex compound.
10. The optoelectronic device according to claim 9, wherein the host material is 4,4'-N, N' -biphenyldicarbazole.
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| JP2022082519A (en) * | 2020-11-23 | 2022-06-02 | 北京夏禾科技有限公司 | Organic electroluminescent material and device thereof |
| WO2023063112A1 (en) | 2021-10-11 | 2023-04-20 | キヤノン株式会社 | Organic compound and organic light-emitting element |
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