CN101538288B - Monomer for organic electro-phosphorescent polymer - Google Patents
Monomer for organic electro-phosphorescent polymer Download PDFInfo
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- CN101538288B CN101538288B CN2009100220369A CN200910022036A CN101538288B CN 101538288 B CN101538288 B CN 101538288B CN 2009100220369 A CN2009100220369 A CN 2009100220369A CN 200910022036 A CN200910022036 A CN 200910022036A CN 101538288 B CN101538288 B CN 101538288B
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- phosphorescent polymer
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Abstract
The invention discloses a monomer for an organic electro-phosphorescent polymer. The monomer for the organic electro-phosphorescent polymer is formed by using end alkene beta-diketone as a ligand and complexing metal iridium ions. The structure of the monomer is given in the below formula, wherein R is a hydrogen atom or a fluorine atom. It proves that the monomer for the organic electro-phosphorescent polymer is an electroluminescent material containing a polymerization activity center and can be used as an organic electroluminescent material or is used for preparing the organic electro-phosphorescent polymer.
Description
Technical field
The present invention relates to a kind of monomer for organic electro-phosphorescent polymer, this monomer for organic electro-phosphorescent polymer is a kind of complex of iridium that contains with end alkene beta-diketon.
Background technology
Development along with the information age, have efficient, energy-conservation, light-weight organic electroluminescent flat-panel screens (OLEDs) and more and more be subjected to people's attention, this type of active illuminating, light, thin, good contrast, the organic electroluminescence device that energy consumption is low have proposed higher requirement to luminescent material.The 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 thin layer crystallization occurs easily when practical application, thereby influences device lifetime.
In order to solve the problem that the small molecules organic electroluminescence device exists, best bet is the synthetic luminescence polymer of design, simultaneously because the polymer organic electroluminescence device manufacture method is simple, cost of manufacture is low, and favorable mechanical character is arranged, and makes it become the research focus.Yet this type of organic electro-phosphorescent polymer 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 monomer for organic electro-phosphorescent polymer is provided, this monomer for organic electro-phosphorescent polymer not only has end alkene polymerization activity center, but also has higher luminous efficiency, 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 monomer for organic electro-phosphorescent polymer is characterized in that, this monomer for organic electro-phosphorescent polymer that makes is the complex of iridium that contains with end alkene beta-diketon, and its general structure is as follows:
Wherein, R is hydrogen atom or trifluoromethyl.
When R is a hydrogen atom, obtain compound two (2-[4-morpholinodithio yl pyridines) [1-(9,9-dihexyl-2-fluorenyl)-12-tridecylene-1,3-diketone] and close iridium, its structural formula is as follows:
When R is a trifluoromethyl, obtain compound two (2-[4-morpholinodithio base-5-5-flumethiazine) [1-(9,9-dihexyl-2-fluorenyl)-12-tridecylene-1,3-diketone] and close iridium, its structural formula is as follows:
The present invention is synthetic with reference to following route:
The experiment proved that monomer for organic electro-phosphorescent polymer 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 spectrogram that compound (2-[4-morpholinodithio yl pyridines) [1-(9,9-dihexyl-2-fluorenyl)-12-tridecylene-1,3-diketone] closes iridium;
Fig. 2 is the spectrogram that compound two (2-[4-morpholinodithio base-5-5-flumethiazine) [1-(9,9-dihexyl-2-fluorenyl)-12-tridecylene-1,3-diketone] closes iridium.
The present invention is described in further detail below in conjunction with embodiment that accompanying drawing and contriver provide.
Embodiment
According to monomer for organic electro-phosphorescent polymer general structure of the present invention, the contriver provides following examples, need to prove, 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 compound two (2-[4-morpholinodithio yl pyridines) [1-(9,9-dihexyl-2-fluorenyl)-12-tridecylene-1,3-diketone] closes iridium (btp)
2Ir (wsh)
1.1 synthetic route
1.2 synthesis step
1.2.1 changing chlorine, two (2-[4-morpholinodithio yl pyridines) close iridium (btp)
4Ir
2Cl
2Synthetic
Under the nitrogen, add 2-thionaphthene yl pyridines 7mmol in the there-necked flask of 250mL successively, three hydration iridous chloride 2.8mmol, 40mL water, 150mL ethylene glycol ethyl ether, back flow reaction 24h.Add 100ml water, have solid to separate out.Filter, dry (btp)
4Ir
2Cl
2It is synthetic to be directly used in down the step.
(1.2.21-9,9-dihexyl-2-fluorenyl)-12-tridecylene-1,3-diketone (wsh) synthetic
Add the 9.3g potassium tert.-butoxide in the 250mL there-necked flask successively, the 2-ethanoyl-9 of 5.0g, 9-dihexyl fluorenes, the own ester of the undecylenic acid of 12.9g stirs 72h under the room temperature.Reaction solution is poured in the 150mL frozen water, fully stirred.Dilute hydrochloric acid with 10% is regulated pH to 5-6, leaves standstill.Tell organic phase and be washed to neutrality, use anhydrous magnesium sulfate drying, the filtering and concentrating mother liquor.Silica gel column chromatography separates (eluent is a normal hexane) and gets 1-(9,9-dihexyl-2-fluorenyl)-12-tridecylene-1,3-diketone 1.8g.
1.2.3 two (2-[4-morpholinodithio yl pyridines) [1-(9,9-dihexyl-2-fluorenyl)-12-tridecylene-1,3-diketone] close iridium (btp)
2Ir's (wsh) is synthetic
Under the nitrogen, add successively in the 250ml there-necked flask (btp)
4Ir
2Cl
20.45mmol, wsh 1.13mmol, salt of wormwood 0.8g, 1,2-ethylene dichloride 100mL, back flow reaction 24h, reacting liquid filtering, organic phase is washed to neutrality, anhydrous magnesium sulfate drying, filtering and concentrating.With normal hexane/methylene dichloride is that the eluent silica gel column chromatography separates, and gets yellow solid.
1.3 structural analysis
Magnetic resonance spectroscopy (
1H-NMR, CDCl
3, 500MHz, δ (ppm)): 8.432 (t, 2H), 7.597～7.684 (m, 4H), 7.575d, 4H), 7.505 (s, 1H), 7.450 (d, 2H), 7.226 (s, 3H), 7.032～6.994 (m, 2H), 6.892～6.857 (m, 2H), 6.785 (t, 1H), 6.252 (t, 2H), 5.880 (s, 1H), 5.790～5.709 (m, 1H), 4.910 (d, 2H), 2.134～1.765 (3m, 8H), 1.460 (s, 2H), 1.336～1.289 (m, 2H), 1.217～1.127 (m, 2H), 1.118～0.909 (m, 18H), 0.729～0.641 (m, 6H), 0.554 (s, 4H).
Infrared spectra (KBr, cm
-1) 3053,1262 (C=C-H); 2925,2851,1474 (CH2-); 1601 (C=O); 1579,1434,758 (pyridines); 909 (thiophene).
Ultimate analysis:
Calculated value (%): C:66.55, H:5.98, N:2.43, S:5.55;
Measured value (%): C:66.58, H:6.02, N:2.44, S:5.54.
Mass spectrum: (1154M
+).
The compound that the above-mentioned reaction of above data acknowledgement obtains is that two (2-thionaphthene yl pyridines) [1-(9,9-dihexyl-2-fluorenyl)-12-tridecylene-1,3-diketone] close iridium.Its structural formula is as follows:
Fluorescence spectrum: with 970CRT type fluorescent spectrophotometer assay, recording the fluorescence spectrum peak wavelength is 612nm, belongs to the ruddiness category, and fluorescence spectrum as shown in Figure 1.
Embodiment 2: preparation compound two (2-[4-morpholinodithio base-5-5-flumethiazine) [1-(9,9-dihexyl-2-fluorenyl)-12-tridecylene-1,3-diketone] closes iridium (btfmpy)
2Ir (wsh)
2.1 synthetic route
2.2 synthesis step
2.2.1 changing chlorine, two (2-[4-morpholinodithio bases-5-5-flumethiazine) close iridium (btfmpy)
4Ir
2Cl
2Synthetic
Under the nitrogen, add 2-benzothienyl-5-5-flumethiazine 7mmol in the there-necked flask of 250mL successively, three hydration iridous chloride 2.8mmol, 40mL water, 150mL ethylene glycol ethyl ether, back flow reaction 24h.Add 100ml water, have solid to separate out.Filter, dry (btfmpy)
4Ir
2Cl
2It is synthetic to be directly used in down the step.
2.2.2 two (2-[4-morpholinodithio bases-5-5-flumethiazine) [1-(9,9-dihexyl-2-fluorenyl)-12-tridecylene-1,3-diketone] close iridium (btfmpy)
2Ir's (wsh) is synthetic
Under the nitrogen, add successively in the 250ml there-necked flask (btfmpy)
4Ir
2Cl
20.45mmol, 1-(9,9-dihexyl-2-fluorenyl)-12-tridecylene-1,3-diketone 1.13mmol, salt of wormwood 0.8g, 1,2-ethylene dichloride 100mL, back flow reaction 24h, reacting liquid filtering, organic phase is washed to neutrality, anhydrous magnesium sulfate drying, filtering and concentrating.With normal hexane/methylene dichloride is that the eluent silica gel column chromatography separates, and gets yellow solid.
2.3 structure is identified
Magnetic resonance spectroscopy (
1H-NMR, CDCl
3, 500MHz, δ (ppm)): 8.728 (s, 1H), 8.666 (s, 1H), 7.016 (d, 2H), 7.715 (t, 4H), 7.661-7.647 (q, 1H), 7.609-7.533 (m, 3H), 7.300-7.253 (q, 3H), 7.161 (t, 2H), 6.911-6.872 (m, 2H), 6.351-6.306 (q, 2H), 5.987 (s, 1H), 5.852-5.771 (m, 1H), 5.012-4.922 (m, 1H), 2.177 (m, 2H), 2.049-1.994 (m, 2H), 1.943-1.883 (m, 4H), 1.529 (s, 2H), 1.448-1.321 (m, 5H), 1.253-1.202 (m, 3H), 1.158-0.973 (m, 20H), 0.772-0.708 (m, 6H).
Infrared spectra (KBr, cm
-1): 3057,2926,2854 (c h bond characteristic absorbance), 1706 (disappearances of enol form change characteristic absorbance), 1611,1547,1514,1493 (aromatic ring characteristic absorbance), 1320 (C-N key characteristic absorbance), 1134 (C-F key characteristic absorbance), 1082 (C-S key characteristic absorbance).
Ultimate analysis:
Calculated value (%): C:61.42, H:5.23, N:2.17, S:4.97;
Measured value (%): C:61.40, H:5.24, N:2.20, S:4.50.
Mass spectrum: (1290M
+).
The compound that the above-mentioned reaction of above data acknowledgement obtains is that two (2-benzothienyls-5-5-flumethiazine) [1-(9,9-dihexyl-2-fluorenyl)-12-tridecylene-1,3-diketone] close iridium, and its structural formula is as follows:
Fluorescence spectrum: with 970CRT type fluorescent spectrophotometer assay, recording the fluorescence spectrum peak wavelength is 632nm, belongs to the ruddiness category, and fluorescence spectrum as shown in Figure 2.
Claims (1)
1. a monomer for organic electro-phosphorescent polymer is characterized in that, this monomer for organic electro-phosphorescent polymer that makes is the complex of iridium that contains with end alkene beta-diketon, and its general structure is as follows:
Wherein, R is hydrogen atom or trifluoromethyl;
When R is a hydrogen atom, obtain compound (2-[4-morpholinodithio yl pyridines) [1-(9,9-dihexyl-2-fluorenyl)-12-tridecylene-1,3-diketone] and close iridium, its structural formula is as follows:
Recording the fluorescence spectrum peak wavelength is 612nm, belongs to the ruddiness category;
When R is a trifluoromethyl, obtain compound two (2-[4-morpholinodithio base-5-5-flumethiazine) [1-(9,9-dihexyl-2-fluorenyl)-12-tridecylene-1,3-diketone] and close iridium, its structural formula is as follows:
Recording the fluorescence spectrum peak wavelength is 632nm, belongs to the ruddiness category.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1554128A (en) * | 2001-06-20 | 2004-12-08 | �Ѻ͵繤��ʽ���� | Light emitting material and organic light-emitting device |
| CN101337875A (en) * | 2008-08-18 | 2009-01-07 | 西安近代化学研究所 | Beta-dione compounds with terminal vinyl group |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1554128A (en) * | 2001-06-20 | 2004-12-08 | �Ѻ͵繤��ʽ���� | Light emitting material and organic light-emitting device |
| CN101337875A (en) * | 2008-08-18 | 2009-01-07 | 西安近代化学研究所 | Beta-dione compounds with terminal vinyl group |
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