CN102108087A - Polymerizable Electrophosphorescent Iridium Complex Monomers - Google Patents
Polymerizable Electrophosphorescent Iridium Complex Monomers Download PDFInfo
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- CN102108087A CN102108087A CN2009101556485A CN200910155648A CN102108087A CN 102108087 A CN102108087 A CN 102108087A CN 2009101556485 A CN2009101556485 A CN 2009101556485A CN 200910155648 A CN200910155648 A CN 200910155648A CN 102108087 A CN102108087 A CN 102108087A
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- iridium
- pyridine
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- electrophosphoresceniridium
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Abstract
本发明公开了一种可聚合的电致磷光铱配合物单体，该可聚合的铱配合物单体是以(C^N)型二齿配体为主配体、4-乙烯基苯甲基乙酰丙酮为辅助配体络合金属铱离子形成，其结构如下式，其中R代表(C^N)型二齿配体。经验证，本发明的铱配合物单体是一种含有聚合活性中心的有机电致发光材料，能够作为有机电致发光材料，或用于制备有机电致磷光聚合物。
The invention discloses a polymerizable electrophosphorescent iridium complex monomer. The polymerizable iridium complex monomer is a (C^N) type bidentate ligand as the main ligand, 4-vinylbenzyl Acetyl acetylacetone is formed by complexing metal iridium ions with an auxiliary ligand, and its structure is as follows, wherein R represents a (C^N) type bidentate ligand. It has been verified that the iridium complex monomer of the present invention is an organic electroluminescent material containing a polymerization active center, and can be used as an organic electroluminescent material or for preparing an organic electroluminescent polymer.
Description
Technical field
The invention belongs to field of organic electroluminescent materials, be specifically related to a kind of polymerisable electrophosphoresceniridium iridium complex monomer.
Background technology
Organic electroluminescence device is as flat panel display of new generation, compare with technique of display in the past, the performance that a lot of excellences are arranged, as wide visual angle, fast response speed, light and approach, high brightness, high-level efficiency and active illuminating, so have broad application prospects in full color demonstration field.At present,, at room temperature have higher luminous efficiency and stronger phosphorescence and become focus (the Advanced Materials of research owing to have short triplet lifetime based on the electromechanical phosphorescent material of complex of iridium, 2008,20,1-5), be widely used in the preparation organic electroluminescence device.
Organic electroluminescence device can be divided into small molecules organic electroluminescence device and polymer organic electroluminescence device according to the difference of its material.The small molecules organic electroluminescence device occurs problems such as thin layer crystallization easily, thereby influences device lifetime in use.In order to solve this type of problem, best bet is the synthetic luminescence polymer of design, serves as basis preparation polymer organic electroluminescence device with it.Polymkeric substance has the favorable mechanical processibility simultaneously, can make device by methods such as spin coating, scraper coating, spray ink Printings, and technology is simple, cost is low, good mechanical property, easily realizes big area and flexible the demonstration, makes it more and more be subjected to people's attention.
Beta-diketon is very high (ε＞10 of a class specific absorbance
4) organic ligand, the title complex that beta-diketon and osmium, iridium, platinum and rare earth form because of the luminescent properties with excellence be always people study focus (Nature, 2009,459,234-239).In order to obtain luminescence polymer, a kind of terms of settlement is to prepare the electrophosphoresceniridium iridium complex monomer by polymerisable beta-diketonate ligand and iridium coordination, and then aggregates into required polymkeric substance.Yet this type of polymerisable electrophosphoresceniridium iridium complex monomeric species seldom at present.
Summary of the invention
Defective or deficiency at above-mentioned prior art existence, the objective of the invention is to, a kind of polymerisable electrophosphoresceniridium iridium complex monomer is provided, this polymerisable electrophosphoresceniridium iridium complex monomer has end alkene polymerization activity center, can be as electroluminescent organic material, or be used to prepare organic electro-phosphorescent polymer.
In order to realize above-mentioned task, the present invention takes following technical solution: a kind of polymerisable electrophosphoresceniridium iridium complex monomer, it is characterized in that, the polymerisable electrophosphoresceniridium iridium complex monomer of this that makes is to be the complex of iridium that contains of assistant ligand with 4-vinyl benzene methyl methyl ethyl diketone, and its structural formula is as follows:
As preferably, described main part R is one of following (C^N) type bidentate ligand:
As preferably, when main part R is 2-p-methylphenyl pyridine, obtains compound two (2-p-methylphenyl pyridine) (4-vinyl benzene methyl methyl ethyl diketone) and close iridium, its structural formula is as follows:
As preferably, when main part R is 2-(2,4 difluorobenzene base) pyridine, obtains compound two [2-(2,4 difluorobenzene base) pyridine] (4-vinyl benzene methyl methyl ethyl diketone) and close iridium, its structural formula is as follows:
As preferably, when main part R is 2-(2 '-thienyl) pyridine, obtains compound two [2-(2 '-thienyl) pyridine] (4-vinyl benzene methyl methyl ethyl diketone) and close iridium, its structural formula is as follows:
As preferably, when main part R is 2-(2 '-benzothienyl) pyridine, obtains compound two [2-(2 '-benzothienyl) pyridine] (4-vinyl benzene methyl methyl ethyl diketone) and close iridium, its structural formula is as follows:
Empirical tests, polymerisable electrophosphoresceniridium iridium complex monomer of the present invention contains the end alkene at polymerization activity center, can further prepare the iridium-containing phosphorescent polymer luminescent material, and can directly use as electroluminescent organic material.
Description of drawings
Fig. 1 is the photoluminescence spectra figure that compound two (2-p-methylphenyl pyridine) (4-vinyl benzene methyl methyl ethyl diketone) closes iridium;
Embodiment
The present invention is described in further detail below in conjunction with embodiment that accompanying drawing and contriver provide.
According to polymerisable electrophosphoresceniridium iridium complex monomer structure general formula of the present invention, the contriver provides following examples, need to prove that these embodiment are mainly used in those skilled in the art to further understanding of the present invention, the invention is not restricted to these embodiment.
Embodiment 1: preparation two (2-p-methylphenyl pyridines) (4-vinyl benzene methyl methyl ethyl diketone) close iridium Ir (ptpy)
2(pvba)
1.1 synthetic route
1.2 synthesis step
1.2.12-p-methylphenyl pyridine iridium dimer [Ir (ptpy)
2Cl]
2Synthetic
In the 250mL round-bottomed flask, add 2.118g (6mmol) hydration iridous chloride, 2.56mL (15mmol) 2-p-methylphenyl pyridine, 90mL ethoxy ethanol and 30mL water are at N
2Be heated to 120 ℃ under the protection, stirring and refluxing reaction 24h.Reaction finishes postcooling to room temperature, remove by filter supernatant liquid, with gained solid methanol wash, then dissolve with methylene dichloride, remove insolubles through suction filtration, gained filtrate adds methanol wash after boiling off solvent again, at last the gained solid is obtained 2-p-methylphenyl pyridine iridium dimer, yield 70.6% through vacuum-drying.
1.2.2 two (2-p-methylphenyl pyridines) (4-vinyl benzene methyl methyl ethyl diketone) close iridium Ir (ptpy)
2Synthesizing (pvba)
In the 50mL round-bottomed flask of reflux condensation mode pipe unit is housed; add 4-vinyl benzene methyl methyl ethyl diketone 86.5mg (0.4mmol), 0.65mg para benzoquinone stopper and complex of iridium dimer 0.226g (0.2mmol); add 20mL2-ethoxy ethanol and 0.212g (2mmol) anhydrous sodium carbonate again; under nitrogen protection, 135 ℃ of backflow 15h.Decompression steamed solvent after reaction finished, and water and absolute ethanol washing promptly get required product Ir (ptpy) through column chromatography for separation more respectively
2(pvba), yield 53%.
1.3 structure is identified
Magnetic resonance spectroscopy: (
1H-NMR, CDCl
3, 400MHz, δ (ppm)): 8.691～6.052 (m, 19H), 5.677～5.151 (m, 2H), 3.412 (s, 2H), 2.095 (s, 6H, Ar-CH
3), 1.788 (s, 6H, CH
3).
Infrared spectra (KBr, cm
-1): 2919 (C-H), 1603 (C=C), 1587 (C=C), 1561 (C=N), 1474 (C=C), 1428,1262,772 (ph-H).
Ultimate analysis: calculated value (%): C, 61.35; H, 4.74; N, 3.77; Measured value (%): C, 61.03; H, 4.61; N, 3.86.
The compound that the above-mentioned reaction of above data acknowledgement obtains is that two (2-p-methylphenyl pyridines) (4-vinyl benzene methyl methyl ethyl diketone) close iridium, and its structural formula is as follows:
1.4 photoluminescence spectra
With Hitachi F-4600 type fluorescent spectrophotometer assay, recording its photoluminescence spectra (Fig. 1) peak wavelength is 533.6nm, belongs to the green glow category.
Embodiment 2: preparation two [2-(2,4 difluorobenzene base) pyridine] (4-vinyl benzene methyl methyl ethyl diketones) close iridium Ir (dfpp)
2(pvba)
Synthetic route is as follows:
Other are with examples of implementation 1, and main part is 2-(2,4 difluorobenzene base) pyridine, have synthesized polymerisable electrophosphoresceniridium iridium complex monomer two [2-(2,4 difluorobenzene base) pyridine] (4-vinyl benzene methyl methyl ethyl diketone) and have closed iridium Ir (dfpp)
2(pvba), other and examples of implementation 1 are similar.Productive rate is 45%.
With Hitachi F-4600 type fluorescent spectrophotometer assay, recording its photoluminescence spectra peak wavelength is 505nm, belongs to the green glow category.
Embodiment 3: iridium Ir (thp) is closed in preparation two [2-(2 '-thienyl) pyridine] (4-vinyl benzene methyl methyl ethyl diketone)
2(pvba)
Synthetic route is as follows:
Other are with examples of implementation 1, and main part is 2-(2 '-thienyl) pyridine, have synthesized polymerisable electrophosphoresceniridium iridium complex monomer two [2-(2 '-thienyl) pyridine] (4-vinyl benzene methyl methyl ethyl diketone) and have closed iridium Ir (thp)
2(pvba), other and examples of implementation 1 are similar.Productive rate is 46%.
With Hitachi F-4600 type fluorescent spectrophotometer assay, recording its photoluminescence spectra peak wavelength is 584nm, belongs to the gold-tinted category.
Embodiment 4: iridium Ir (btp) is closed in preparation two [2-(2 '-benzothienyl) pyridine] (4-vinyl benzene methyl methyl ethyl diketone)
2(pvba)
Synthetic route is as follows:
Other are with examples of implementation 1, and main part is 2-(2 '-benzothienyl) pyridine, have synthesized polymerisable electrophosphoresceniridium iridium complex monomer two [2-(2 '-benzothienyl) pyridine] (4-vinyl benzene methyl methyl ethyl diketone) and have closed iridium Ir (btp)
2(pvba), other and examples of implementation 1 are similar.Productive rate is 41%.
With Hitachi F-4600 type fluorescent spectrophotometer assay, recording its photoluminescence spectra peak wavelength is 634nm, belongs to the ruddiness category.
Claims (6)
1. a polymerisable electrophosphoresceniridium iridium complex monomer is characterized in that, the polymerisable electrophosphoresceniridium iridium complex monomer that makes is to be the complex of iridium that contains of assistant ligand with 4-vinyl benzene methyl methyl ethyl diketone, and its structural formula is as follows:
Wherein main part R is (C^N) type bidentate ligand.
2. polymerisable electrophosphoresceniridium iridium complex monomer as claimed in claim 1 is characterized in that, main part R is one of following (C^N) type bidentate ligand:
3. polymerisable electrophosphoresceniridium iridium complex monomer as claimed in claim 2, it is characterized in that, when main part R is 2-p-methylphenyl pyridine, obtain compound two (2-p-methylphenyl pyridine) (4-vinyl benzene methyl methyl ethyl diketone) and close iridium, its structural formula is as follows:
4. polymerisable electrophosphoresceniridium iridium complex monomer as claimed in claim 2 is characterized in that, when main part R is 2-(2, the 4-difluorophenyl) during pyridine, obtain compound two [2-(2,4 difluorobenzene base) pyridine] (4-vinyl benzene methyl methyl ethyl diketone) and close iridium, its structural formula is as follows:
5. polymerisable electrophosphoresceniridium iridium complex monomer as claimed in claim 2, it is characterized in that, when main part R is 2-(2 '-thienyl) pyridine, obtain compound two [2-(2 '-thienyl) pyridine] (4-vinyl benzene methyl methyl ethyl diketone) and close iridium, its structural formula is as follows:
6. polymerisable electrophosphoresceniridium iridium complex monomer as claimed in claim 2, it is characterized in that, when main part R is 2-(2 '-benzothienyl) pyridine, obtain compound two [2-(2 '-benzothienyl) pyridine] (4-vinyl benzene methyl methyl ethyl diketone) and close iridium, its structural formula is as follows:
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295923A (en) * | 2011-07-11 | 2011-12-28 | 宁波大学 | N-vinylcarbazole/iridium complex copolymerized electrophosphorescent material and preparation method thereof |
| CN105859787A (en) * | 2015-01-20 | 2016-08-17 | 上海和辉光电有限公司 | Soluble phosphorescence OLED material and polymer used as luminescent material |
| JP2019112387A (en) * | 2017-09-01 | 2019-07-11 | 株式会社Ｋｙｕｌｕｘ | Raw material for synthesizing organic light-emitting element material, and compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1828965A (en) * | 2004-11-27 | 2006-09-06 | 三星Sdi株式会社 | organic light emitting device |
| CN101608114A (en) * | 2008-06-17 | 2009-12-23 | 宁波大学 | A kind of polymer iridium complex electrophosphorescent material and its synthesis method |
-
2009
- 2009-12-24 CN CN2009101556485A patent/CN102108087A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1828965A (en) * | 2004-11-27 | 2006-09-06 | 三星Sdi株式会社 | organic light emitting device |
| CN101608114A (en) * | 2008-06-17 | 2009-12-23 | 宁波大学 | A kind of polymer iridium complex electrophosphorescent material and its synthesis method |
Non-Patent Citations (4)
| Title |
|---|
| SHIZUO TOKITO等，: "High-efficiency phosphorescent polymer light-emitting devices", 《ORGANIC ELECTRONICS》 * |
| WEN YONG LAI等，: "A study on the preparation and photophysical properties of an iridium(III) complexed homopolymer", 《J. MATER. CHEM.》 * |
| 徐清等,: "新型含铱共聚物的合成及表征", 《功能材料》 * |
| 徐清等,: "铱配合物Ir(ptpy)2(VBA)的合成及表征", 《光谱实验室》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295923A (en) * | 2011-07-11 | 2011-12-28 | 宁波大学 | N-vinylcarbazole/iridium complex copolymerized electrophosphorescent material and preparation method thereof |
| CN105859787A (en) * | 2015-01-20 | 2016-08-17 | 上海和辉光电有限公司 | Soluble phosphorescence OLED material and polymer used as luminescent material |
| JP2019112387A (en) * | 2017-09-01 | 2019-07-11 | 株式会社Ｋｙｕｌｕｘ | Raw material for synthesizing organic light-emitting element material, and compound |
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Application publication date: 20110629 |