CN101531899B - Iridium containing phosphorescent polymer organic electroluminescence material - Google Patents
Iridium containing phosphorescent polymer organic electroluminescence material Download PDFInfo
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- CN101531899B CN101531899B CN2009100220439A CN200910022043A CN101531899B CN 101531899 B CN101531899 B CN 101531899B CN 2009100220439 A CN2009100220439 A CN 2009100220439A CN 200910022043 A CN200910022043 A CN 200910022043A CN 101531899 B CN101531899 B CN 101531899B
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- iridium
- organic electroluminescence
- phosphorescent polymer
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Abstract
The invention discloses an iridium containing phosphorescent polymer organic electroluminescence material used for an organic electroluminescence device, and a general formula of a structure of the material is shown as following, wherein R is hydrogen atoms or methyl-trifluoro; and m and n are number of units of a vinyl-carbazole unit of random copolymerization and an ethylene structural unit containing an iridium complex, and the ratio of the m to the n is (99.8-97.0) to (0.2-3.0).
Description
Technical field
The invention belongs to electroluminescent organic material, relate to a kind of luminescent material, be specifically related to a kind of iridium containing phosphorescent polymer organic electroluminescence material, be mainly used in organic electroluminescence device.
Background technology
Along with the development of information age, have efficient, energy-conservation, light-weight organic electroluminescent flat-panel screens (OLEDs) and big area white-light illuminating and more and more receive people's attention, and become the research focus in this year.This type of active illuminating, light, thin, good contrast, the organic electroluminescence device that energy consumption is low have proposed higher requirement to material.
People such as Baldo [M.A.Baldo; S.Lamansky, P.E.Burrows, M.E.Thompson; S.R.Forrest; Very high-efficiency green organic light-emitting devices based on electrophosphorescence, Appl.Phys.Lett.1999,75:4-6.] 1999 years with small molecules phosphor material Ir (ppy)
3Mix among the material of main part CBP, the device luminous efficiency is 28cd/A, and power is 31lm/W, emission peak position 510nm, and its performance causes everybody extensive concern to the metal complexes luminescent material immediately considerably beyond the electroluminescent fluorescent luminescent device.But this based on micromolecular device, there is crystalline polamer in luminescent material in device preparation and work, makes the life-span of device reduce, and organic molecule device preparation simultaneously needs vacuum evaporation, complex process, and production cost is high.
People such as Gong [X.Gong, M.R.Robinson, J.C.Ostrowski; D.Moses, G.C.Bazan, A.J.Heeger; High-efficiency polymer-based electrophosphorescent devices, Adv.Mater.2002,14:581-585.] with Ir (DPF)
3Mix in PVK and the PBD mixture and obtain the phosphorescent polymer device, its external quantum efficiency reaches 10%, and current efficiency is 36cd/A, luminous peak position 550nm, and high-high brightness surpasses 8000cd/m
2This preparation technology is simple through the phosphor material solution spin coating in polymkeric substance in little minute of mixing, and is beneficial to preparation large area display spare and illuminating device, but has phenomenon of phase separation, causes device performance and life-span to be reduced.
In order to solve the problem that doping small molecules phosphorescent polymer device exists; Best approach is the synthetic phosphorescent polymer of design, and just small molecules phosphorescence luminescent ligand compound and main polymer monomer copolymerization form the macromolecular compound of the main unit that contains phosphorescent complexes unit and transmission energy.In the special conjugated polymers of this type, specific charge transfer or emission group can directly be connected on the polymer backbone or be connected on the non-conjugated polymeric thing skeleton as side group.The advantage of this method is to guarantee to control multipolymer glow color and conjugate length, and owing to can form amorphous polymer, can effectively suppress the self-quenching of triplet excitons, the stability of raising material.
The polymkeric substance that contains the heavy metal phosphorescent complexes; Be small molecules heavy metal phosphorescent complexes and polymer monomer copolymerization; Formation contains the unitary phosphorescent polymer of heavy metal complex; In conjunction with high-luminous-efficiency and the easy manufacture craft of polymer luminescent material of heavy metal phosphorescent complexes, the input of just attracting to get more and more both at home and abroad investigator and large enterprises has become a current research focus.
But the phosphorescent polymer material as electroluminescent material still is fewer at present, is restricting the development of the cheap display device of high-performance.
Summary of the invention
Defective or deficiency to the above-mentioned background technology exists the objective of the invention is to, and a kind of iridium-containing phosphorescent polymer luminescent material with good stability, film-forming properties and luminescent properties are provided, for the phosphorescent polymer material provides the new kind selected.
In order to realize above-mentioned task, the present invention takes following technical solution:
A kind of iridium containing phosphorescent polymer organic electroluminescence material is characterized in that, the general structure of this iridium containing phosphorescent polymer organic electroluminescence material that makes is following:
Wherein R is Wasserstoffatoms, trifluoromethyl; M, n are the carbazyl ethylene unit and the unitary unit number of vinyl structure that contains complex of iridium, m: n=(99.8～97.0)/(0.2～3.0) of random copolymerization.
When R is a Wasserstoffatoms, obtain a preferred iridium containing phosphorescent polymer organic electroluminescence material PF3, its structural formula is:
M wherein, n are the carbazyl ethylene unit and the unitary unit number of vinyl structure that contains complex of iridium, m: n=(99.8～97.0)/(0.2～3.0) of random copolymerization.
When R is a trifluoromethyl, obtain another preferred iridium containing phosphorescent polymer organic electroluminescence material PF4, its structural formula is:
M wherein, n are the carbazyl ethylene unit and the unitary unit number of vinyl structure that contains complex of iridium, m: n=(99.8～97.0)/(0.2～3.0) of random copolymerization.
The iridium-containing phosphorescent polymer material that is used for organic electroluminescent of the present invention; The number-average molecular weight of this phosphorescent polymer is between 20000～4000; The present invention characterizes through the thermal property of DTA row to material, proves that this material has excellent thermomechanical property (heat decomposition temperature＞370 ℃), good stability; And has good solubility; Reach the effect of telomerized polymer emission wavelength through the structure of regulating the iridium metal complex part, PF3, the emission wavelength of PF4 be respectively 617nm, 645nm (± 2nm) about.Such polymer luminescent material has had the excellent properties of polymkeric substance and phosphor material concurrently, helps developing the flat-panel screens and the large area lighting device of superior performance of future generation.
Description of drawings
Fig. 1 is the fluorescence spectrum figure of iridium containing phosphorescent polymer organic electroluminescence material PF3;
Fig. 2 is the fluorescence spectrum figure of iridium containing phosphorescent polymer organic electroluminescence material PF4.
Below in conjunction with embodiment the present invention is done further detailed description.
Embodiment
According to the general structure of iridium containing phosphorescent polymer organic electroluminescence material of the present invention, the main raw material for preparing this iridium containing phosphorescent polymer organic electroluminescence material is:
Three hydration iridous chlorides are available from Xi'An Catalyst Chemical Co., Ltd.;
Ligand 1-methyl isophthalic acid 3-tetradecene-2, the 4-diketone, (application number: method 200810147093.5) is synthetic for its synthesized reference one Chinese patent application;
2-[4-morpholinodithio yl pyridines, 2-thionaphthene-5-5-flumethiazine, (Maoliang Xu et.al., Optical Materials 28 (2006), and is 1025-1028) synthetic for reference.
Below be the embodiment that the contriver provides, 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 iridium containing phosphorescent polymer organic electroluminescence material PF3
1.1 two (2-[4-morpholinodithio yl pyridines) [1-(9,9-dihexyl-2-fluorenyl)-13-tetradecene-2,4-diketone] close the synthetic of iridium
Synthetic route:
Compound method:
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 dipolymer (1).Directly be used for going on foot down synthetic.
Under the nitrogen, add dipolymer (1) 0.45mmol in the 250ml there-necked flask successively, 1-(9,9-dihexyl-2-fluorenyl)-13-tetradecene-2; 4-diketone 1.13mmol, salt of wormwood 0.8g, 1; 2-ethylene dichloride 100mL, back flow reaction 24h, reacting liquid filtering; The organic phase washing is 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).
1.2 structure is identified
Magnetic resonance spectroscopy (
1H-NMR, CDCl
3, 500MHz, δ (ppm)): 8.432 (t, 2H), 7.597～7.684 (m, 4H), 7.575 (d, 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).
Ir 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)-13-tetradecene-2,4-diketone] close iridium.
1.3 iridium containing phosphorescent polymer organic electroluminescence material PF3's is synthetic
Under the nitrogen protection; [1-(9 with two (the 2-[4-morpholinodithio yl pyridines) of 0.02mmol; 9-dihexyl-2-fluorenyl)-13-tetradecene-2; The 4-diketone] close iridium and N-VCz and be dissolved in the 10ml tetrahydrofuran solvent according to 0.2%: 99.8% mol ratio, add 4%mol Diisopropyl azodicarboxylate (AIBN) and under reflux temperature, react 10h.After reaction finishes, steam THF, be dissolved in then in the 5ml chloroform, pour into and carry out sedimentation in the methyl alcohol, filter.Filter cake places apparatus,Soxhlet's with methyl alcohol extracting 48h.Solids takes out the back 30 ℃ of following vacuum-dryings.Obtain the red solid powder, called after iridium containing phosphorescent polymer organic electroluminescence material PF3, its structural formula is following:
Wherein, R is a Wasserstoffatoms, and m, n are the carbazyl ethylene unit and the unitary unit number of vinyl structure that contains complex of iridium, m: n=(99.8～97.0)/(0.2～3.0) of random copolymerization.
1.3 fluorescence spectrum test
Fluorescence spectrum is with 970CRT type fluorescent spectrophotometer assay, and it is 20mg/mL that sample is dissolved in tetrahydrofuran solution concentration, gets rid of with KW-4A type sol evenning machine and processes film, and test is all carried out under room temperature.Test result is as shown in Figure 1, and maximum emission wavelength is 617nm.
Embodiment 2: preparation iridium containing phosphorescent polymer organic electroluminescence material PF4
2.1 two (2-[4-morpholinodithio bases-5-5-flumethiazine) [1-(9,9-dihexyl-2-fluorenyl)-13-tetradecene-2,4-diketone] close the synthetic of iridium
Synthetic route:
Compound method:
Under the nitrogen, in the there-necked flask of 250mL, add 2-benzothienyl-5-5-flumethiazine 7mmol 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 dipolymer (3).Directly be used for going on foot down synthetic.
Under the nitrogen, add dipolymer (3) 0.45mmol in the 250ml there-necked flask successively, 1-(9,9-dihexyl-2-fluorenyl)-13-tetradecene-2; 4-diketone 1.13mmol, salt of wormwood 0.8g, 1; 2-ethylene dichloride 100mL, back flow reaction 24h, reacting liquid filtering; The organic phase washing is 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 (4).
2.2 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).
Ir 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)-13-tetradecene-2,4-diketone] close iridium.
2.3 iridium containing phosphorescent polymer organic electroluminescence material PF4's is synthetic
Under the nitrogen protection; [1-(9 with two (the 2-[4-morpholinodithio bases-5-5-flumethiazine) of 0.02mmol; 9-dihexyl-2-fluorenyl)-13-tetradecene-2; The 4-diketone] close iridium and N-VCz and be dissolved in the 10ml tetrahydrofuran solvent according to 0.2%: 99.8% mol ratio, add 4%mol Diisopropyl azodicarboxylate (AIBN) and under reflux temperature, react 10h.After reaction finishes, steam THF, be dissolved in then in the 5ml chloroform, pour into and carry out sedimentation in the methyl alcohol, filter.Filter cake places apparatus,Soxhlet's with methyl alcohol extracting 48h.Solids takes out the back 30 ℃ of following vacuum-dryings.Get the pink solid powder, called after iridium containing phosphorescent polymer organic electroluminescence material PF4, its structural formula is following:
M wherein, n are the carbazyl ethylene unit and the unitary unit number of vinyl structure that contains complex of iridium, m: n=(99.8～97.0)/(0.2～3.0) of random copolymerization.
2.3 fluorescence spectrum test
Fluorescence spectrum is with 970CRT type fluorescent spectrophotometer assay, and it is 20mg/mL that sample is dissolved in tetrahydrofuran solution concentration, gets rid of with KW-4A type sol evenning machine and processes film, and test is all carried out under room temperature.Test result is as shown in Figure 2, and maximum emission wavelength is 645nm.
Claims (1)
1. an iridium containing phosphorescent polymer organic electroluminescence material is characterized in that, the general structure of this iridium containing phosphorescent polymer organic electroluminescence material that makes is following:
Wherein R is Wasserstoffatoms or trifluoromethyl; M, n are the carbazyl ethylene unit and the unitary unit number of vinyl structure that contains complex of iridium, m: n=(99.8～97.0)/(0.2～3.0) of random copolymerization;
When R is a Wasserstoffatoms, obtain iridium containing phosphorescent polymer organic electroluminescence material PF3, its structural formula is following:
M wherein, n are the carbazyl ethylene unit and the unitary unit number of vinyl structure that contains complex of iridium, m: n=(99.8～97.0)/(0.2～3.0) of random copolymerization;
When R is a trifluoromethyl, obtain iridium containing phosphorescent polymer organic electroluminescence material PF4, its structural formula is following:
M wherein, n are the carbazyl ethylene unit and the unitary unit number of vinyl structure that contains complex of iridium, m: n=(99.8～97.0)/(0.2～3.0) of random copolymerization.
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| Tokito S. et al..High-efficiency phosphorescent polymer light-emitting devices.《Organic Electronics》.2003,第4卷105-111. * |
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