CN104059631B - A kind of containing iridium polymkeric substance red light material and synthetic method thereof - Google Patents
A kind of containing iridium polymkeric substance red light material and synthetic method thereof Download PDFInfo
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- CN104059631B CN104059631B CN201310111763.9A CN201310111763A CN104059631B CN 104059631 B CN104059631 B CN 104059631B CN 201310111763 A CN201310111763 A CN 201310111763A CN 104059631 B CN104059631 B CN 104059631B
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- iridium
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Abstract
The present invention discloses a kind of fluorenes, pyridine thiophene, complex of iridium terpolymer electromechanical phosphorescent material, it is characterised in that: structural formula as shown in the formula. the present invention adopts two-[(the bromo-thiophene of 4-)-phenylpyridine]-β-heptadione complex of iridium monomers and 9, 9-dioctyl-2, 7-bis-bromine base fluorenes and 9, 9-dioctyl fluorene-2, 7-hypoboric acid two (1, ammediol) ester three kinds of monomers carry out copolymerization, obtain the conjugated polymers that main chain contains complex of iridium, this polymkeric substance is the saturated red light material of a kind of efficient stable, in addition, owing to introducing β-heptadione ligand and dioctyl fluorene unit, phosphor material is made also to have solvability good, the feature that film forming properties is good, can by revolving painting, the method making devices such as coating, complete processing is simple, good mechanical property, easily realize big area and Flexible Displays,。
Description
Technical field
The present invention relates to a kind of polymer luminescent material and synthetic method thereof, especially relate to a kind of novel containing iridium polymkeric substance red light material and relevant synthetic method thereof.
Technical background
Under the effect of electric field, the phenomenon that electric energy is directly changed into luminous energy by organic materials is called organic electroluminescent (EL). Report brightness height and the low double-deck organic electroluminescence device of operating voltage from people such as Tang in 1987 since, membrane electro luminescent device obtains and develops rapidly, and electroluminescent organic material arouses great concern due to the performance of its excellence. Wherein complex of iridium luminescent material due to its triplet lifetime short, have good phosphorescence performance, become the maximum heavy metal complex luminescent material of research. Due to small molecules complex of iridium there is easy crystallization, the shortcoming such as be separated, people have started to pay attention to the research containing iridium polymkeric substance phosphor material. These materials had both had the good characteristics of luminescence of small molecules complex of iridium, possessed again the mechanical property of superpolymer excellence and good film-forming properties, thus can more easily realize large-area displays, widen the range of application of complex of iridium.
Synthetic method containing iridium polymkeric substance has a variety of, the Suzuki polymerization etc. of the such as radical polymerization of small molecules complex of iridium vinyl monomer or living polymerization, ring-opening metathesis polymerization, small molecules complex of iridium monomer and other monomers. By the method for Suzuki coupling, small molecule partner unit being introduced polymer is a kind of method obtaining efficient stable PLED, and the easy modularization synthesis of gained material, can distinguish photoelectric properties and the processing characteristics of controlled material, and effective Inhibitory molecules is assembled.Such as, the people such as Park have obtained a kind of containing iridium polymkeric substance green phosphorescent material PFIrptb025 with Suzuki coupling method, and when voltage is 11V, brightness is 2260cd/m2, when voltage is 7.5V, efficiency is 1.1cd/A (Macromolecules, 2009,42:5551-5557).
The iridium polymkeric substance phosphor material that contains of synthesis at present is mainly yellow light and green light material, and the research of red light material also exists very big deficiency, mainly carry out trap-charge produce enough red shifts and make polymkeric substance send saturated ruddiness owing to not designing suitable narrow band gap metal complexes. Therefore the polymkeric substance phosphor material of the more saturated red of design and synthesis is the current problem still needing to solve.
Summary of the invention
According to the technical problem that above-mentioned background technology is mentioned, it is an object of the present invention to provide one and there is good stability, film-forming properties and luminescent properties containing iridium polymkeric substance red light material, the synthetic method that this contains iridium polymkeric substance red light material is provided simultaneously.
The novel structural formula containing iridium polymkeric substance red light material of the present invention is:
Described polymkeric substance phosphor material is by two-[(the bromo-thiophene of 4-)-phenylpyridine]-β-heptadione complex of iridium, 9; 9-dioctyl-2; 7-bis-bromine base fluorenes and 9; 9-dioctyl fluorene-2; 7-hypoboric acid two (1; ammediol) ester copolymerization under lucifuge, protection of inert gas obtains, and solvent for use is toluene or dimethylbenzene, and catalyzer is Pd (PPh3)4, alkali is the tetraethyl ammonium hydroxide aqueous solution, and copolymerization temperature is 90-105 DEG C, and the reaction times is 3-4d, and in reactant, complex of iridium monomer molar content is 1%-10%.
Compared with prior art, it is an advantage of the current invention that, two-[(the bromo-thiophene of 4-)-phenylpyridine]-β-heptadione complex of iridium monomers and 9,9-dioctyl-2,7-two bromine base fluorenes and 9,9-dioctyl fluorene-2,7-hypoboric acid two (1, ammediol) ester carries out copolymerization, obtains the conjugated polymers that main chain contains complex of iridium, and this polymkeric substance is a kind of efficient stable, the emission wavelength saturated red light material near 650nm. In addition owing to introducing β-heptadione ligand and dioctyl fluorene unit, phosphor material is also had solvability is good, film forming properties is good feature, can by revolving the method making devices such as painting, coating, complete processing is simple, good mechanical property, it is easy to realize big area and Flexible Displays.
Accompanying drawing explanation
Fig. 1 is the synthesis path of this polymkeric substance phosphor material;
Fig. 2 be polymkeric substance phosphor material prepared by embodiment 1 magnetic resonance spectroscopy (1H-NMR) spectrogram;
Fig. 3 is the thermogravimetric curve of the red phosphorescence material prepared by embodiment 1.
Embodiment
The synthesis (synthetic route is shown in Fig. 1) of red phosphorescence material of the present invention and the mensuration of physicals is illustrated further below by embodiment.
Embodiment 1:
Measure in the there-necked flask that 10mL toluene (logical nitrogen sonic oscillation 10min) joins 25mL, take two-[(the bromo-thiophene of 4-)-phenylpyridine]-β-heptadione complex of iridium monomer (0.0036g, 0.00358mmol), 9,9-dioctyl-2,7-two bromine base fluorenes (0.0962g, 0.175mmol), 9,9-dioctyl fluorene-2,7-hypoboric acid two (1,3-propylene glycol) ester (0.1g, 0.179mmol), Pd (PPh3)4(0.0062g; 0.00537mmol) put into there-necked flask, in removal system after air, add 1mL tetraethyl ammonium hydroxide solution; under nitrogen protection; 100 DEG C of lucifuge reaction 72h, add 9,9-dioctyl fluorene-2; 7-hypoboric acid two (1; ammediol) ester (0.005g, 0.00895mmol) (dissolving of 1.5mL toluene) continuation reaction 12h, add 2mL bromobenzene and continue reaction 12h.After reaction terminates, the palladium catalyst being filtered to remove in reaction, after evaporating major part solvent with Rotary Evaporators, the sedimentation in methyl alcohol of remaining solution, takes out and is filtered dry dry crude product, and acetone surname extraction obtains yellow solid. M is recorded by GPCn=13500, it is λ=654nm that spectrophotofluorometer records maximum emission wavelength.
Embodiment 2:
Measure in the there-necked flask that 10mL toluene (logical nitrogen sonic oscillation 10min) joins 25mL, take two-[(the bromo-thiophene of 4-)-phenylpyridine]-β-heptadione complex of iridium monomer (0.0072g, 0.00716mmol), 9,9-dioctyl-2,7-bis-bromine base fluorenes (0.0942g, 0.172mmol), take 9,9-dioctyl fluorene-2,7-hypoboric acid two (1,3-propylene glycol) ester (0.1g, 0.179mmol), Pd (PPh3)4(0.0062g; 0.00537mmol) put into there-necked flask, in removal system after air, add 1mL tetraethyl ammonium hydroxide solution; under nitrogen protection; 90 DEG C of lucifuge reaction 60h, add 9,9-dioctyl fluorene-2; 7-hypoboric acid two (1; ammediol) ester (0.005g, 0.00895mmol) (dissolving of 1.5mL toluene) continuation reaction 6h, add 2mL bromobenzene and continue reaction 6h. After reaction terminates, the palladium catalyst being filtered to remove in reaction, after evaporating major part solvent with Rotary Evaporators, the sedimentation in methyl alcohol of remaining solution, takes out and is filtered dry dry crude product, and acetone surname extraction obtains yellow solid. M is recorded by GPCn=12000, it is λ=656nm that spectrophotofluorometer records maximum emission wavelength.
Embodiment 3:
Measure in the there-necked flask that 10mL dimethylbenzene (logical nitrogen sonic oscillation 10min) joins 25mL, take two-[(the bromo-thiophene of 4-)-phenylpyridine]-β-heptadione complex of iridium monomer (0.0180g, 0.0179mmol), 9,9-dioctyl-2,7-bis-bromine base fluorenes (0.0889g, 0.162mmol), take 9,9-dioctyl fluorene-2,7-hypoboric acid two (1,3-propylene glycol) ester (0.1g, 0.179mmol), Pd (PPh3)4(0.0062g; 0.00537mmol) put into bottle, in removal system after air, add 1mL tetraethyl ammonium hydroxide solution; under nitrogen protection; 105 DEG C of lucifuge reaction 64h, add 9,9-dioctyl fluorene-2; 7-hypoboric acid two (1; ammediol) ester (0.005g, 0.00895mmol) (dissolving of 1.5mL toluene) continuation reaction 12h, add 2mL bromobenzene and continue reaction 12h. After reaction terminates, the palladium catalyst being filtered to remove in reaction, after evaporating major part solvent with Rotary Evaporators, the sedimentation in methyl alcohol of remaining solution, takes out and is filtered dry dry crude product, and acetone surname extraction obtains yellow solid. M is recorded by GPCn=10800, spectrophotofluorometer records maximum absorption and is emitted as λ=658nm.
Embodiment 4:
Measure in the there-necked flask that 10mL toluene (logical nitrogen sonic oscillation 10min) joins 25mL, take two-[(the bromo-thiophene of 4-)-phenylpyridine]-β-heptadione complex of iridium monomer (0.0360g, 0.0358mmol), 9,9-dioctyl-2,7-two bromine base fluorenes (0.0786g, 0.143mmol), 9,9-dioctyl fluorene-2,7-hypoboric acid two (1,3-propylene glycol) ester (0.1g, 0.179mmol), Pd (PPh3)4(0.0062g; 0.00537mmol) put into there-necked flask, in removal system after air, add 1mL tetraethyl ammonium hydroxide solution; under nitrogen protection; 100 DEG C of lucifuge reaction 72h, add 9,9-dioctyl fluorene-2; 7-hypoboric acid two (1; ammediol) ester (0.005g, 0.00895mmol) (dissolving of 1.5mL toluene) continuation reaction 12h, add 2mL bromobenzene and continue reaction 12h.After reaction terminates, the palladium catalyst being filtered to remove in reaction, after evaporating major part solvent with Rotary Evaporators, the sedimentation in methyl alcohol of remaining solution, takes out and is filtered dry dry crude product, and acetone surname extraction obtains yellow solid. M is recorded by GPCn=9800, it is λ=655nm that spectrophotofluorometer records maximum emission wavelength.
Embodiment 5:
By core magnetic (1H-NMR) polymkeric substance phosphor material is carried out structural characterization, by its optical physics performance being characterized by fluorescence, ultraviolet spectrometer, by the thermostability of thermogravimetric analysis test material.
Claims (3)
1., containing an iridium polymkeric substance red light material, its structural formula is:
2. the synthetic method containing iridium polymkeric substance red light material according to claim 1; it is characterized in that: by two-[(the bromo-thiophene of 4-)-phenylpyridine]-β-heptadione complex of iridium, 9; 9-dioctyl-2; 7-bis-bromine base fluorenes and 9; the copolymerization under lucifuge, protection of inert gas of 9-dioctyl fluorene-2,7-hypoboric acid two (1,3-propylene glycol) ester obtains; solvent for use is toluene or dimethylbenzene, and catalyzer is Pd (PPh3)4, alkali is the tetraethyl ammonium hydroxide aqueous solution, and copolymerization temperature is 90-105 DEG C, and the reaction times is 3-4d.
3. a kind of synthetic method containing iridium polymkeric substance red light material according to claim 2, it is characterised in that: two-[(the bromo-thiophene of 4-)-phenylpyridine]-β-heptadione complex of iridium account for the 1%-10% of reaction monomers total mole number.
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| CN1671818A (en) * | 2002-07-30 | 2005-09-21 | E·I·内穆尔杜邦公司 | Metallic complexes covalently bound to conjugated polymers and electronic devices containing such compositions |
| CN1671819A (en) * | 2002-06-04 | 2005-09-21 | H·C·施塔克股份有限公司 | Phosphorescent and luminescent conjugated polymers and their use in electroluminescent assemblies |
| CN101125913A (en) * | 2007-09-18 | 2008-02-20 | 华南理工大学 | 9,9-disubstitution-3,6-fluorenes polymer, preparing method and application thereof |
| CN101998983A (en) * | 2007-12-17 | 2011-03-30 | 通用电气公司 | Emissive polymeric materials for optoelectronic devices |
| CN102295923A (en) * | 2011-07-11 | 2011-12-28 | 宁波大学 | N-vinylcarbazole/iridium complex copolymerized electrophosphorescent material and preparation method thereof |
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Patent Citations (5)
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| CN1671819A (en) * | 2002-06-04 | 2005-09-21 | H·C·施塔克股份有限公司 | Phosphorescent and luminescent conjugated polymers and their use in electroluminescent assemblies |
| CN1671818A (en) * | 2002-07-30 | 2005-09-21 | E·I·内穆尔杜邦公司 | Metallic complexes covalently bound to conjugated polymers and electronic devices containing such compositions |
| CN101125913A (en) * | 2007-09-18 | 2008-02-20 | 华南理工大学 | 9,9-disubstitution-3,6-fluorenes polymer, preparing method and application thereof |
| CN101998983A (en) * | 2007-12-17 | 2011-03-30 | 通用电气公司 | Emissive polymeric materials for optoelectronic devices |
| CN102295923A (en) * | 2011-07-11 | 2011-12-28 | 宁波大学 | N-vinylcarbazole/iridium complex copolymerized electrophosphorescent material and preparation method thereof |
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| Conjugated Polymers Bearing Iridium Complexes for Triplet Photovoltaic Devices;Gisela L. Schulz 等;《Chem. Mater.》;20080725;第20卷;5351-5355 * |
| Enhancement of Phosphorescence of Ir Complexes Bound to Conjugated Polymers: Increasing the Triplet Level of the Main Chain;Gisela L.Schulz 等;《Macromolecules》;20061205;第39卷;9157-9165 * |
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