CN1246417C - Electroluminescent organic material and its application - Google Patents
Electroluminescent organic material and its application Download PDFInfo
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Abstract
The present invention relates to organic electroluminescent material and application thereof. The electroluminescent organic material belongs to the technical field of electronic material. The material is a central atom and is the metal complex of a gallium atom, which comprises five coordinates of a three-tooth ligand. The organic electroluminescent material is characterized in that the material has the structure of a right formula, wherein I, II and III respectively represent an aromatic ring or a heterocyclic compound and a substituted derivative thereof. The material of the present invention has the advantages of high vitrification temperature, high thermal stability, easy formation of good amorphous thin film, strong fluorescence in solution and a solid film, high fluorescence quantum efficiency, priority electron transmission, cavity block, etc. The material can also be used as a luminous body, including an independent luminous layer, a body doped by dye to emit light, or doped dye to emit light.
Description
Technical field:
The present invention relates to a kind of electroluminescent organic material, belong to technical field of electronic materials.
Background technology:
Now, along with the arriving of Development of Multimedia Technology and information society, more and more higher to the flat-panel monitor performance demands.In recent years emerging three kinds of technique of display: plasma display, Field Emission Display and display of organic electroluminescence (OLED) have all remedied the deficiency of cathode tube and liquid-crystal display to a certain extent.Wherein, a series of advantages such as OLED has from main light emission, low voltage direct drive, solidifies entirely, the visual angle is wide, color is abundant, compare with liquid-crystal display, OLED does not need backlight, and the visual angle is big, and power is low, its response speed reaches 1000 times of liquid-crystal display, its manufacturing cost but is lower than the liquid-crystal display of equal resolving power, and therefore, display of organic electroluminescence certainly will have broad application prospects.
The typical structure of OLED comprises cathode layer, anode layer, and the organic function layer between this is two-layer, can comprise one or more functional layers in electron transfer layer, hole transmission layer and the luminescent layer in the organic function layer.The material that is used for organic electroluminescent accordingly also can be divided into according to its function of being born in device: electron transport material, hole mobile material and luminescent material three major types.The people such as C.W.Tang of Kodak in 1987 adopt bilayer structure to make luminescent layer with oxine aluminium (Alq3), as hole transmission layer, have obtained the high brightness organic EL device that DC low-voltage drives with aromatic diamines.This breakthrough makes organic electroluminescence device become the focus of current luminescent device research.Wherein oxine aluminium has concurrently luminous and electric transmission two big functions, and its employing has initiative historic significance (Appl.Phys.Lett., 1987,51 (913); Coordination Chemistry Reviews, 171 (1998) 161-174).But the fluorescence quantum efficiency of Alq3 itself and electroluminescent efficiency are still lower, and the development of organic electroluminescent technology also depends on the perfect of the exploitation of novel electroluminescent material and device architecture.
The derivative of various thereupon oxine aluminium is developed and is used for Study on Organic Light-Emitting Devices, wherein is mostly to modify to improve its performance doing on its part.Y.Hamada (IEEE transactions on electron devices, 1997,44,1208) novelty is introduced the salicylidene leucine as tridentate ligand first, though in solution,, do not obtain the solid luminescent material having observed the intensive blue-fluorescence.People such as Shao Yan adopt stable fragrant tridentate ligand to replace original fats tridentate ligand in patent CN1258710A, have obtained (the adjacent amine phenol of salicylidene)-(oxine) that thermostability and film-forming properties improve a lot and have closed aluminium (III) (Al (Saph)-q) and derivative thereof.Report (Chem.Lett. is also arranged in the literature, 2000,1068-1069 and Adv.Mater.Opt.Electron., 10 (6), 283-286), adopt adjacent hydroxyl aromatic aldehyde to contract adjacent hydroxy aromatic amine, replaced two oxine parts among the Alq3 as tridentate ligand, can increase the asymmetry of molecule, thus the film forming properties of the material that improves.But what the central metallic ions of Al (Saph)-q and derivative thereof still adopted in the existing patented technology is metallic aluminium, the experiment proved that its purifying products is very difficult.
The derivative of another kind of oxine aluminium is to change its central metallic ions, as adopt Zn, Mg, Be, Ga, In to replace Al, glow color, efficient and stability to title complex all has certain change like this, through experiment relatively, wherein good comprehensive properties mainly is that central metallic ions is the title complex of Ga, Zn and Be.Oxine gallium (Gaq
3) glow color be yellow-green colour, the spectrum peak about 553nm, have higher brightness.People such as P.E.Burrowsd (.Appl.Phys.Lett.64 (20), 1994) comparative study the oxine metal complexes of Al, Ga, In, Sc, find at same device architecture (ITO/TPD (20nm)/Mq3 (40nm)/Mg: Ag), adopt Gaq
3Device not only showed the external quantum efficiency suitable with the device of Alq3, and have the lower energy efficiency that opens bright voltage and Geng Gao (device than Alq3 exceeds 50%).People (J.Phys.D.34 such as Shuit-tong Lee, 30-35,2001) comparative study with Al, Ga and In are that central metal ion oxine metal complexes is respectively as bulk material, the doping red dye 4-4-dicyano methylene radical-2-tertiary butyl-6-(1,1,7,7-tetramethyl--julolidine-9-vinyl)-4H-pyrans (DCJMTB), use N, N '-phenylbenzene-N, N '-two (aminomethyl phenyl)-1,1 '-xenyl-4, (ITO/TPD/MQ3: DCJMTB/MQ3/Mg: performance Ag), result find that equally the device that uses Gaq3 to make bulk doped DCJMTB has saturated red emission to 4 '-diamines (TPD) as the red electroluminescent device of hole mobile material, and higher current efficiency is arranged, surpassed the device that Alq3 makes bulk doped DCJMTB.In addition, Sapochak (J.Phys.Chem, 100,17766-17771) with Andreas Elschner (Adv.Mater.23, (3), 1811,2001) etc. the people has reported the research to the pentacoordinate compound of the methyl substituted oxine gallium of 2-, finds that it also shows good electroluminescent properties.This shows that in numerous materials of attempting substitute for Al q3, the title complex of gallium has showed superior performance, is acknowledged as a most promising class material.Therefore it is very significant the title complex of new type of metal gallium being carried out deep research.
Summary of the invention:
The objective of the invention is to propose a kind of novel electroluminescent organic material, this material is a metal complexes, can improve and of the prior artly be the metal complexes of part with the oxine and be the problem that central metal ion metal complexes exists with Al, the present invention seeks to improve the fluorescence quantum efficiency and the electroluminescent efficiency of material, improve the material filming performance, overcome the easy crystalline shortcoming of material, and the assurance material is purified easily.
The present invention proposes a kind of novel electroluminescent organic material, this material is that a kind of central atom is the metal complexes with tridentate ligand of gallium atom, it is characterized in that, this luminescent material have below shown in structure:
In the said structure formula, I, II, III represent the derivative of aromatic nucleus or heterogeneous ring compound and replacement thereof respectively, wherein the aromatic nucleus at I place can be oxine, 4-hydroxyl-1, a kind of in 5-naphthyridines, 5-hydroxyl-quinoxaline, 2-(2-hydroxy phenyl) benzoxazole, 2-(2-hydroxy phenyl) benzoglyoxaline, 2-(2-hydroxy phenyl) benzothiazole, 10-hydroxy benzo quinoline or the pyridine-2-formic acid; The aromatic nucleus at II, III place can be in phenyl ring, naphthalene nucleus or the phenanthrene ring a kind of, perhaps for containing a kind of in heteroatomic aromatic nucleus such as pyridine, thiazole or the carbazole, wherein I, II, III is last that one or more substituting groups can be arranged, substituting group can be a kind of in hydrogen atom, alkyl, iso-alkyl, alkoxyl group, nitro, cyano group, amino, halogen atom, aromatic base, furans, thiophene, pyrroles or the pyridine.
In the electroluminescent organic material general structure of the present invention, ligand i wherein can be oxine, 4-hydroxyl-1, a kind of in 5-naphthyridines, 5-hydroxyl-quinoxaline, 2-(2-hydroxy phenyl) benzoxazole, 2-(2-hydroxy phenyl) benzoglyoxaline, 2-(2-hydroxy phenyl) benzothiazole, 10-hydroxy benzo quinoline or the pyridine-2-formaldehyde etc.Wherein the substituting group on the I can be a kind of in hydrogen atom, alkyl, iso-alkyl, alkoxyl group, nitro, cyano group, amino, halogen atom, aromatic base, furans, thiophene, pyrroles or the pyridine.
According to the difference of ligand i structure, luminescent material of the present invention roughly has 8 class formations, shown in following structural formula i-viii:
Among the structure i-viii as implied above, when ligand i I, III are preferred typical compound during respectively for phenyl ring, i.e. compound i-1-viii-1, it is as follows for structure:
Structural formula is the compound of i, and when ligand i wherein is an oxine, when ligand i I, III were respectively the derivative of condensed ring such as phenyl ring, naphthalene nucleus or phenanthrene ring and replacement thereof, preferred 25 kinds of compound i-the 1-i-25 structure was as follows:
General structure is the compound of i, when ligand i wherein is the oxine that replaces, and ligand i I, when III was phenyl ring, preferred compound i-the 26-i-35 structure was as follows:
General structure is the compound of ii, and when ligand i wherein be a 4-hydroxyl-1 for what replace, when 5-naphthyridines, ligand i I, III were respectively the derivative of condensed ring such as phenyl ring, naphthalene nucleus or phenanthrene ring and replacement thereof, preferably compound i i-1-ii-2 structure was as follows:
General structure is the compound of iii, and when ligand i wherein is 5-hydroxyl-quinoxaline, when ligand i I, III were respectively the derivative of condensed ring such as phenyl ring, naphthalene nucleus or phenanthrene ring and replacement thereof, preferred compound i ii-1-iii-3 structure was as follows:
General structure is the compound of iv, when 2-(2-hydroxy phenyl) benzoxazole and the derivative thereof of ligand i wherein for replacing, when ligand i I, III were respectively the derivative of condensed ring such as phenyl ring, naphthalene nucleus or phenanthrene ring and replacement thereof, preferred compound i v-1-iv-5 structure was as follows:
General structure is the compound of v, when 2-(2-hydroxy phenyl) benzoglyoxaline and the derivative thereof of ligand i wherein for replacing, when ligand i I, III were respectively the derivative of condensed ring such as phenyl ring, naphthalene nucleus or phenanthrene ring and replacement thereof, preferred compound v-1-v-12 structure was as follows:
General structure is the compound of vi, when 2-(2-hydroxy phenyl) benzothiazole and the derivative thereof of ligand i wherein for replacing, when ligand i I, III were respectively the derivative of condensed ring such as phenyl ring, naphthalene nucleus or phenanthrene ring and replacement thereof, preferred compound vi-1-vi-6 structure was as follows:
General structure is the compound of vii, and when ligand i wherein is a 10-hydroxy benzo quinoline, when ligand i I, III were respectively the derivative of condensed ring such as phenyl ring, naphthalene nucleus or phenanthrene ring and replacement thereof, preferred compound vii-1-vii-2 structure was as follows:
General structure is the compound of viii, and when wherein ligand i is pyridine-2-formic acid, when ligand i I, III were respectively the derivative of condensed ring such as phenyl ring, naphthalene nucleus or phenanthrene ring and replacement thereof, preferred compound viii-1 structure was as follows:
The present invention uses Ga to substitute the central metallic ions Al of the metal complexes in the prior art, thereby for the selection of part provides bigger degree of freedom, so that develop the metal complexes that contains more eurypalynous part, further expanded the kind of the organic compound that can be used for preparing organic electroluminescence device like this.
Material in of the present invention has the following advantages: the second-order transition temperature height, and Heat stability is good forms good amorphous thin film easily, and this material all has stronger fluorescence, fluorescence quantum efficiency height in solution and solid film.
Experiment finds that the complex compound that contains tridentate ligand is the high organometallic complex of class stability, and they are difficult for crystallization mostly simultaneously, are easy to form the indefiniteness film.Very strong for the preparation electroluminescent device.They have high glass transition, the second-order transition temperature that wherein preferred (oxine)-(the adjacent aniline phenol of salicylidene) closes gallium (III) (compound i) has reached 477K, exceeds 30K than the second-order transition temperature 448K of the best luminescent material Alq3 that generally acknowledges at present.
Electroluminescent organic material of the present invention has prioritised transmission electronics, blocking hole, and simultaneously can also be used as twinkler, comprises independent one-tenth luminescent layer, and is perhaps luminous as the bulk doped dyestuff, perhaps as adulterated dyestuff and luminous.As luminescent material, the fluorescence quantum efficiency of its intensity of fluorescence is to weigh the important indicator of its characteristics of luminescence.Experiment finds that electroluminescent organic material of the present invention all has very strong fluorescence under solution and solid film state.It is 0.318 that wherein preferred (oxine)-(the adjacent aniline phenol of salicylidene) closes the fluorescence quantum efficiency of gallium (III) (compound i) in dimethyl formamide solution, has exceeded 1.74 times than the fluorescence quantum efficiency (0.116) of the Alq3 under the similarity condition.Such material belongs to the luminous metal complexes of part, and along with the change of part, the luminous of its title complex also can be mobile to some extent accordingly, can realize the emission from the green glow to ruddiness.
Utilize the organic electroluminescence device of luminescent material preparation of the present invention can show high brightness, high efficiency high-performance.Through experiment confirm, no matter be the organic electroluminescence device that material of the present invention is prepared as luminescent layer separately, still be as bulk material with material of the present invention, the organic electroluminescence device that mixes up the dyestuff preparation all has very high luminosity and luminous efficiency, as with material of the present invention as bulk material, mix up as the red dye of 4-4-dicyano methylene radical-2-methyl-6-dimethylamino styryl-4H-pyrans (DCM) series and can realize saturated red emission.
Description of drawings:
Fig. 1 is the mass spectrum of the compound i-1 of the present invention's preparation.
Fig. 2 is the mass spectrum of the compound i-2 of the present invention's preparation.
Fig. 3 is the mass spectrum of the compound i v-1 of the present invention's preparation.
Fig. 4 is absorption spectrum (a) and the fluorescence emission spectrum (b) (excitation wavelength be 390nm) of compound i-1 in DMF solution of the present invention's preparation.
Fig. 5 is the device that utilizes The compounds of this invention i-1 preparation
The current-voltage curve (a) of TTO/NPB (40nm)/i-1 (40nm)/Mg: Ag (10: 1) and brightness-voltage curve (b).
Fig. 6 is the device that utilizes The compounds of this invention i-1 preparation
The electroluminescent spectrum figure of TTO/NPB (40nm)/i-1 (40nm)/Mg: Ag (10: 1).
Fig. 7 is the ruddiness device that utilizes The compounds of this invention i-1 preparation
TTO/NPB (30nm)/i-1:DCJTB (2%, 40nm)/the electroluminescent spectrum figure of Mg: Ag (10: 1).
Embodiment:
Below introduce embodiments of the present invention.
The embodiment of compound sample preparation:
Electroluminescent organic material of the present invention adopts synthetic method preparation in organic solvent.The step that adopts comprises two portions: the one, and corresponding tridentate ligand synthetic, the 2nd, target title complex synthetic.
The synthetic method of the synthetic employing azomethine (Schiff base) of the relevant tridentate ligand of the first step wherein.Detailed process be will contain the aromatic aldehyde and the direct Hybrid Heating reaction of the aromatic amine solid phase that contains adjacent hydroxyl of the adjacent hydroxyl that measures ratio, perhaps heating reflux reaction in alcoholic solvent all can obtain the thick product of corresponding azomethine.By the method for recrystallization in organic solvent, be easy to obtain the very high product of purity then.
The inorganic salt of the synthetic employing gallium of the target compound in second step and corresponding part are in the system of alcohol and water, by adding the generation of alkali control product.Thick product is purified through the method for subregion distillation and is got final product high-purityly product.
Embodiment 1: compound i-1 synthetic
Synthesizing of part salicylidene Ortho-Aminophenol:
Take by weighing salicylic aldehyde 1.22 grams (0.01 mole) and put into reaction flask, add equimolar Ortho-Aminophenol 1.09 grams (0.01 mole), direct heating, promptly there is red material to produce, Deng the reaction finish after, use ethyl alcohol recrystallization can obtain acicular product, i.e. salicylidene Ortho-Aminophenol, productive rate is 85%.
Synthesizing of compound i-1:
In the there-necked flask of whipping appts is housed, add the ethanolic soln of 20 milliliter of 0.88 gram (0.005 mole) anhydrous gallium trichloride.0.73 gram (0.005 mole) oxine is dissolved in the mixing solutions that 20ml ethanol and 0.43 restrains (0.005 mole) hexahydropyridine fully, this solution is under agitation slowly splashed in the above-mentioned solution, add the back and continue to stir 5 minutes.1.065 gram (0.005 mole) salicylidene Ortho-Aminophenols are dissolved in fully the mixing solutions of 100ml ethanol and 0.85 gram (0.01 mole) hexahydropyridine, under agitation slowly be added dropwise to this solution in the above-mentioned reaction soln, add the back and continue to stir 1 hour, place ageing with the dark place then.At last this solution is added deionized water isopyknic with it, have a large amount of flockss to produce immediately, put into refrigerator ageing 10 hours, suction filtration goes out solid, is drying to obtain thick product under the infrared lamp, and productive rate is 85%.Obtain bright orange through subregion distillation purification again and get solid, i.e. (oxine)-(the adjacent aniline phenol of salicylidene) closes the pure product of gallium (III) (compound i-1).
Results of elemental analyses is: C 62.28%, and H 3.52%, and N 6.52%, and O 11.53%; With theoretical value C 62.13%, H 3.51%, and N 6.52%, and O 11.53% coincide fine.The mass spectroscopy molecular weight is M
+=425, referring to accompanying drawing 1.In addition it is mixed with the DMF solution of 10-5mol/L, measures UV, visible light and absorb and fluorescence emission spectrum, see also accompanying drawing 4.It is 204 ℃ that the DSC test can get its second-order transition temperature.
Embodiment 2: compound i-2 synthetic
Method according to compound i-1 is synthetic, and tridentate ligand wherein adopts the synthetic of part 2-hydroxyl-1-naphthylmethylene Ortho-Aminophenol to get final product.The mass spectroscopy figure that obtains pure product after the distillation of product subregion sees also accompanying drawing 2.Mass spectrum: m/e, 475; Ultimate analysis: measuring C:65.60%, H:3.49%N:5.80%; Theoretical value: C:65.68%, H:3.58%, N:5.89%
Embodiment 3: compound i-6 synthetic:
Synthetic according to the method for compound i-1, tridentate ligand wherein adopts the salicylaldhyde 2-hydroxyl-naphthalidine that contracts to get final product.Mass spectrum: m/e, 475; Ultimate analysis: measuring (%) C:65.61, H:3.52, N:5.92; Theoretical value (%): C:65.68, H:3.58, N:5.89.
Embodiment 4: compound i-8 synthetic
Method according to compound i-1 is synthetic, and tridentate ligand wherein adopts 2-hydroxyl-1-naphthylmethylene 3-hydroxyl-2-naphthylamines to get final product.Mass spectrum: m/e, 525; Ultimate analysis: measuring C:68.50, H:3.59, N:5.30; Theoretical value: C:68.57, H:3.62, N:5.33.
Embodiment 5: compound i-9 synthetic
Method according to compound i-1 is synthetic, and tridentate ligand wherein adopts 2-hydroxyl-1-naphthylmethylene 2-hydroxyl-naphthalidine to get final product.Mass spectrum: m/e, 525; Ultimate analysis: measuring C:68.51, H:3.58, N:5.25; Theoretical value: C:68.57, H:3.62, N:5.33.
Embodiment 6: compound i-19 synthetic
Method according to compound i-1 is synthetic, and tridentate ligand wherein adopts 3-hydroxyl-2-naphthylmethylene 3-hydroxyl-2-naphthylamines to get final product.Mass spectrum: m/e, 525; Ultimate analysis: measuring C:68.53, H:3.59, N:5.35; Theoretical value: C:68.57, H:3.62, N:5.33.
Embodiment 7: compound i-26 synthetic
Method according to compound i-1 is synthetic, adopts 5-fluoro-oxine to replace oxine and gets final product.Mass spectrum: m/e, 443; Ultimate analysis: measuring C:59.52, H:4.32, N:6.30; Theoretical value: C:5959, H:4.29, N:6.32.
Embodiment 8: compound i-27 synthetic
Method according to compound i-1 is synthetic, adopts 5-chloro-oxine to replace oxine and gets final product.Mass spectrum: m/e, 459.5; Ultimate analysis: measuring C:57.40, H:4.20, N:6.01; Theoretical value: C:57.45, H:4.13, N:6.09
Embodiment 9: compound i-28 synthetic.
Method according to compound i-1 is synthetic, adopts 5-cyano group-oxine to replace oxine and gets final product.Mass spectrum: m/e, 450; Ultimate analysis: measuring C:61.30, H:4.15, N:9.25; Theoretical value: C:61.33, H:4.22, N:9.33.
Embodiment 10: compound i-32 synthetic
Method according to compound i-1 is synthetic, adopts 5,6, and 7-three fluoro-oxines are replaced oxine and got final product.Mass spectrum: m/e, 479; Ultimate analysis: measuring C:55.09, H:2.49, N:5.81; Theoretical value: C:55.11, H:2.51, N:5.85.
Embodiment 11: compound i-34 synthetic.
Method according to compound i-1 is synthetic, adopts 5-chloro-oxine to replace oxine, and wherein tridentate ligand adopts 2-hydroxyl-1-naphthylmethylene 3-hydroxyl-2-naphthylamines to get final product.Mass spectrum: m/e, 509.5; Ultimate analysis: measuring C:61.23, H:3.15, N:5.52; Theoretical value: C:61.24, H:3.14, N:5.50
Embodiment 12: compound i-35 synthetic.
Method according to compound i-1 is synthetic, adopts 5-fluoro-oxine to replace oxine, and tridentate ligand wherein adopts 2-hydroxyl-1-naphthylmethylene 2-hydroxyl-naphthalidine to get final product.Mass spectrum: 543; Ultimate analysis: measuring C:66.29, H:3.31, N:5.15; Theoretical value: C:66.30, H:3.32, N:5.16.
Embodiment 13: compound i i-1's is synthetic
Method according to compound i-1 is synthetic, adopts 4-hydroxyl-1, and the 5-naphthyridines is replaced oxine and got final product.Mass spectrum: m/e, 426; Ultimate analysis: measuring C:59.10, H:3.20, N:9.81; Theoretical value: C:59.15, H:3.29, N:9.86.
Embodiment 14: compound i i-2's is synthetic.
Method according to compound i-1 is synthetic, adopts 4-hydroxyl-1, and the 5-naphthyridines is replaced oxine, and tridentate ligand wherein adopts 2-hydroxyl-1-naphthylmethylene ortho-aminophenol to get final product.Mass spectrum: m/e, 476 ultimate analyses: measuring C:63.01, H:3.35, N:8.79; Theoretical value: C:63.03, H:3.36, N:8.82.
Embodiment 15: compound i ii-1's is synthetic
Method according to compound i-1 is synthetic, adopts 5-hydroxyl-quinoxaline to replace oxine and gets final product.Mass spectrum: m/e, 426; Ultimate analysis: measuring C:59.11, H:3.21, N:9.79; Theoretical value: C:59.15, H:3.29, N:9.86.
Embodiment 16: compound i ii-2's is synthetic
Method according to compound i-1 is synthetic, adopts 5-hydroxyl-quinoxaline to replace oxine, and tridentate ligand wherein adopts 2-hydroxyl-1-naphthylmethylene ortho-aminophenol to get final product.Mass spectrum: m/e, 476; Ultimate analysis: measuring C:63.00, H:3.33, N:8.75; Theoretical value: C:63.03, H:3.36, N:8.82.
Embodiment 17: compound i ii-3's is synthetic
Method according to compound i-1 is synthetic, adopts 5-hydroxyl-quinoxaline to replace oxine, and tridentate ligand wherein adopts 2-hydroxyl-1-naphthylmethylene 3-hydroxyl-2-naphthylamines to get final product.Mass spectrum: m/e, 526; Ultimate analysis: measuring C:66.12, H:3.39, N:7.91; Theoretical value: C:66.16, H:3.42, N:7.99.
Embodiment 18: compound i v-1's is synthetic
Method according to compound i-1 is synthetic, and (2-hydroxy phenyl) benzoxazole is replaced oxine and got final product to adopt 2-.Its mass spectrum is referring to accompanying drawing 6.Mass spectrum: m/e, 491; Ultimate analysis: measuring C:63.39, H:3.40, N:5.62; Theoretical value: C:63.41, H:3.46, N:5.69.
Embodiment 19: compound i v-2's is synthetic
Method according to compound i-1 is synthetic, and (2-hydroxy phenyl) benzoxazole is replaced oxine, and tridentate ligand wherein adopts 2-hydroxyl-1-naphthylmethylene ortho-aminophenol to adopt 2-.Mass spectrum: m/e, 541; Ultimate analysis: measuring C:66.50, H:3.49, N:5.15; Theoretical value: C:66.54, H:3.51, N:5.18
Embodiment 20: compound i v-3's is synthetic
Method according to compound i-1 is synthetic, and (2-hydroxyl-3, the phenyl) benzoxazole that the 5-difluoro replaces is replaced oxine and got final product to adopt 2-.Mass spectrum: m/e, 527; Ultimate analysis: measuring C:59.15, H:2.84, N:5.29; Theoretical value: C:59.20, H:2.85, N:5.31
Embodiment 21: compound i v-4's is synthetic
Method according to compound i-1 is synthetic, and (2-hydroxyl-4, the phenyl) benzoxazole that the 6-difluoro replaces is replaced oxine and got final product to adopt 2-.Mass spectrum: m/e, 527; Ultimate analysis: measuring C:59.16, H:2.83, N:5.31; Theoretical value: C:59.20, H:2.85, N:5.31.
Embodiment 22: compound i v-5's is synthetic
Method according to compound i-1 is synthetic, and (2-hydroxyl-3,4, the phenyl) benzoxazole that the 5-trifluoro replaces is replaced oxine and got final product to adopt 2-.Mass spectrum: m/e, 545; Ultimate analysis: measuring C:57.19, H:2.45, N:5.10; Theoretical value: C:57.25, H:2.57, N:5.14.
Embodiment 23: compound v-1's is synthetic
Method according to compound i-1 is synthetic, adopts 2-(2-hydroxy phenyl) benzoglyoxaline to replace oxine and gets final product.Mass spectrum: m/e, 490; Ultimate analysis: measuring C:63.65, H:3.65, N:8.52; Theoretical value: C:63.67, H:3.67, N:8.57.
Embodiment 24: compound v-2's is synthetic
Method according to compound i-1 is synthetic, adopts 1-methyl-2-(2-hydroxy phenyl) benzoglyoxaline to replace oxine and gets final product.Mass spectrum: m/e, 504; Ultimate analysis: measuring C:64.25, H:3.90, N:8.30; Theoretical value: C:64.29, H:3.97, N:8.33.
Embodiment 25: compound v-3's is synthetic
Method according to compound i-1 is synthetic, adopts 1-phenyl-2-(2-hydroxy phenyl) benzoglyoxaline to replace oxine and gets final product.Mass spectrum: m/e, 568; Ultimate analysis: measuring C:67.59, H:4.02, N:7.35; Theoretical value: C:67.61, H:4.05, N:7.39.
Embodiment 26: compound v-4's is synthetic
Method according to compound i-1 is synthetic, adopts 2-(2-hydroxy phenyl) benzoglyoxaline to replace oxine.Wherein tridentate ligand adopts 2-hydroxyl-1-naphthylmethylene ortho-aminophenol to get final product.Mass spectrum: m/e, 540; Ultimate analysis: measuring C66.60: H:3.72, N:7.80; Theoretical value: C:66.67, H:3.70, N:7.78
Embodiment 27: compound v-6 is synthetic
Method according to compound i-1 is synthetic, adopts 1-phenyl-2-(2-hydroxy phenyl) benzoglyoxaline to replace oxine, and tridentate ligand wherein adopts the synthetic of part 2-hydroxyl-1-naphthylmethylene Ortho-Aminophenol to get final product.Mass spectrum: m/e, 617; Ultimate analysis: measuring C:69.99, H:4.02, N:6.78; Theoretical value: C:70.01, H:4.05, N:6.81.
Embodiment 28: compound v-7's is synthetic
Method according to compound i-1 is synthetic, adopts 1-methyl-2-(2-hydroxyl-3,5-two fluoro-phenyl) benzoglyoxaline to replace oxine and gets final product.Mass spectrum: m/e, 540; Ultimate analysis: measuring C:59.98, H:3.30, N:7.81; Theoretical value: C:60.00, H:3.33, N:7.78
Embodiment 29: compound v-8's is synthetic
Method according to compound i-1 is synthetic, adopts 1-methyl-2-(2-hydroxyl-4,6-two fluoro-phenyl) benzoglyoxaline to replace oxine and gets final product.Mass spectrum: m/e, 540; Ultimate analysis: measuring C:59.97, H:3.28, N:7.75; Theoretical value: C:60.00, H:3.33, N:7.78.
Embodiment 30: compound v-9 is synthetic
Method according to compound i-1 is synthetic, adopts 2-(2-hydroxyl-3,4,5,6-tetrafluoro-phenyl) benzoglyoxaline to replace oxine and gets final product.Mass spectrum: m/e, 562; Ultimate analysis: measuring C:55.50, H:2.47, N:7.45; Theoretical value: C:55.52, H:2.49, N:7.47
Embodiment 31: compound v-10's is synthetic
Method according to compound i-1 is synthetic, adopts 1-methyl-2-(2-hydroxyl-3,4,5,6-tetrafluoro-phenyl) benzoglyoxaline to replace oxine and gets final product.Mass spectrum: m/e, 576; Ultimate analysis: measuring C:56.20, H:2.75, N:7.29; Theoretical value: C:56.25, H:2.78, N:7.29
Embodiment 32: compound v-11's is synthetic
Method according to compound i-1 is synthetic, adopts 2-(2-hydroxyl-naphthyl) benzoglyoxaline to replace oxine and gets final product.Mass spectrum: m/e, 540; Ultimate analysis: measuring C:66.65, H:3.71, N:7.81; Theoretical value: C:66.67, H:3.70, N:7.78.
Embodiment 33: compound v-12's is synthetic
Method according to compound i-1 is synthetic, adopts 1-methyl-2-(2-hydroxyl-naphthyl) benzoglyoxaline to replace oxine and gets final product.Mass spectrum: m/e, 554; Ultimate analysis: measuring C:67.14, H:3.98, N:7.55; Theoretical value: C:67.15, H:3.97, N:7.58.
Embodiment 34: compound vi-1's is synthetic
Method according to compound i-1 is synthetic, adopts 2-(2-hydroxyl-phenyl) benzothiazole to replace oxine and gets final product.Mass spectrum: m/e, 507; Ultimate analysis: measuring C:61.50, H:3.36, N:5.50; Theoretical value: C:61.54, H:3.35, N:5.52.
Embodiment 35: compound vi-2's is synthetic
Method according to compound i-1 is synthetic, adopts 2-(2-hydroxyl-phenyl) benzothiazole to replace oxine, and tridentate ligand wherein adopts 2-hydroxyl-1-naphthylmethylene ortho-aminophenol to get final product.Mass spectrum: m/e, 557; Ultimate analysis: measuring C:64.61, H:34.10, N:5.01; Theoretical value: C:64.63, H:34.11, N:5.03
Embodiment 36: compound vi-3's is synthetic
Method according to compound i-1 is synthetic, adopts 2-(2-hydroxyl-3,5-two fluoro-phenyl) benzothiazole to replace oxine and gets final product.Mass spectrum: m/e, 543; Ultimate analysis: measuring C:57.45, H:2.75, N:5.15; Theoretical value: C:57.46, H:2.76, N:5.16.
Embodiment 37: compound vi-4's is synthetic
Method according to compound i-1 is synthetic, adopts 2-(2-hydroxyl-4,6-two fluoro-phenyl) benzothiazole to replace oxine and gets final product.Mass spectrum: m/e, 543; Ultimate analysis: measuring C:57.44, H:2.74, N:5.15; Theoretical value: C:57.46, H:2.76, N:5.16.
Embodiment 38: compound vi-5's is synthetic
Method according to compound i-1 is synthetic, adopts 2-(2-hydroxyl-3,4,5,6-tetrafluoro-phenyl) benzothiazole to replace oxine and gets final product.Mass spectrum: m/e, 579; Ultimate analysis: measuring C:53.87, H:2.23, N:4.80; Theoretical value: C:53.89, H:2.25, N:4.84.
Embodiment 39: compound vi-6's is synthetic
Method according to compound i-1 is synthetic, adopts 2-(2-hydroxyl-naphthyl) benzothiazole to replace oxine and gets final product.Mass spectrum: 557; Ultimate analysis: measuring C:64.62, H:34.09, N:5.01; Theoretical value: C:64.63, H:34.11, N:5.03
Embodiment 40: compound vii-1's is synthetic
Method according to compound i-1 is synthetic, adopts 10-hydroxy benzo quinoline to replace oxine and gets final product.Mass spectrum: m/e, 475; Ultimate analysis: measuring C:65.67, H:3.55, N:5.87; Theoretical value: C:65.68, H:3.58, N:5.89.
Embodiment 41: compound vii-2's is synthetic
Method according to compound i-1 is synthetic, adopts 10-hydroxy benzo quinoline to replace oxine, and tridentate ligand wherein adopts 2-hydroxyl-1-naphthylmethylene ortho-aminophenol to get final product.Mass spectrum: m/e, 525; Ultimate analysis: measuring C:68.49, H:3.57, N:5.26; Theoretical value: C:68.57, H:3.62, N:5.33.
Embodiment 42: compound viii-1's is synthetic
Method according to compound i-1 is synthetic, adopts pyridine-2-formic acid to replace oxine and gets final product.Mass spectrum: m/e, 403; Ultimate analysis: measuring C:56.59, H:3.24, N:6.94; Theoretical value: C:56.58, H:3.23, N:6.95.
Organic electroluminescence device embodiment:
Embodiment 43: adopt compound i-1 to make the luminescent layer material separately, prepared electroluminescent device, its structure is: ITO/NPB (40nm)/i-1 (40nm)/Mg: Ag
On the glass substrate that an Indium sesquioxide-stannic oxide that cleaned (ITO) covers, method by vacuum-evaporation is the hole mobile material N of continuous evaporating-plating 40nm successively, N '-phenylbenzene-N, N '-two (N-phenyl-1-naphthylamine)-benzidine (NPB), the metal M g of compound i-1 among luminescent material the present invention of 40nm ((oxine)-(the adjacent aniline phenol of salicylidene) closes gallium (III)) and 200nm: the alloy of Ag (10: 1) is made negative electrode.The The performance test results of this device is as follows: opening bright voltage is 3.5V, and maximum emission wavelength is 578nm, and high-high brightness is 4400cd/m
2(under the 25V).Its current-voltage curve and brightness-voltage curve see also accompanying drawing 5, and electroluminescent spectrum is referring to accompanying drawing 6.
Embodiment 44: adopt compound i-1 to make bulk material, and doping red dye such as DCJTB, the preparation red electroluminescent device, its device architecture is:
ITO/NPB(40nm)/i-1：DCJTB(2％)(40nm)/Mg∶Ag。
On the glass substrate that an Indium sesquioxide-stannic oxide that cleaned (ITO) covers, method by vacuum-evaporation is the hole mobile material N of continuous evaporating-plating 30nm successively, N '-phenylbenzene-N, N '-two (N-phenyl-1-naphthylamine)-benzidine (NPB), the luminescent layer of 40nm is that the red dye of the compound i-1 and 2% (mass percent) among the present invention and the alloy of the metal M g of 200nm: Ag (10: 1) are made negative electrode.The The performance test results of this device is as follows: opening bright voltage is 2.5V, and the luminescence center wavelength is 644nm, and its chromaticity coordinates is (0.67,0.33), is pure ruddiness.Device brightness when 24V is 2980cd/m
2, electroluminescent spectrum sees also accompanying drawing 7.
Although describe the present invention in conjunction with the preferred embodiments, but the present invention is not limited to the foregoing description, be to be understood that, claims have been summarized scope of the present invention, under the guiding of the present invention's design, it should be appreciated by one skilled in the art that the certain change to the various embodiments of the present invention scheme is carried out all will be covered by the spirit and scope of claims of the present invention.
Claims (11)
1. electroluminescent organic material, this material is that a kind of central atom is the metal complexes that contains tridentate ligand of gallium atom, it is characterized in that this luminescent material has following structure:
In the said structure formula, the part at I, II and III place is represented the derivative of aromatic nucleus or heterogeneous ring compound and replacement thereof respectively, wherein the aromatic nucleus at the two tooth part places at I place is selected from oxine, 4-hydroxyl-1,5-naphthyridines, 5-hydroxyl-quinoxaline, 2-(a kind of in 2-hydroxy phenyl) benzoxazole, 2-(2-hydroxy phenyl) benzoglyoxaline, 2-(2-hydroxy phenyl) benzothiazole, 10-hydroxy benzo quinoline or the pyridine-2-formic acid; The aromatic nucleus at II, III place is selected from a kind of in phenyl ring, naphthalene nucleus, phenanthrene ring, pyridine, thiazole or the carbazole, wherein I, II, III is last that one or more substituting groups can be arranged, substituting group is selected from a kind of in hydrogen atom, alkyl, iso-alkyl, alkoxyl group, nitro, cyano group, amino, halogen atom, the aromatic base that contains 6-20 carbon atom, furans, thiophene, pyrroles or the pyridine.
2. a kind of electroluminescent organic material according to claim 1 is characterized in that, the two tooth parts at wherein said I place are oxine, and II, III are respectively a kind of in phenyl ring, naphthalene nucleus or the phenanthrene ring.
3. a kind of electroluminescent organic material according to claim 1 is characterized in that, the oxine of the two tooth parts at wherein said I place for replacing, and II and III are phenyl ring.
4. a kind of electroluminescent organic material according to claim 1 is characterized in that, wherein the two tooth parts at I place are 4-hydroxyl-1, and 5-naphthyridines, II, III are respectively a kind of in phenyl ring, naphthalene nucleus or the phenanthrene ring.
5. a kind of electroluminescent organic material according to claim 1 is characterized in that, wherein the two tooth parts at I place are 5-hydroxyl-quinoxaline, and II, III are respectively a kind of in phenyl ring, naphthalene nucleus or the phenanthrene ring.
6. a kind of electroluminescent organic material according to claim 1 is characterized in that, wherein the two tooth parts at I place are that (2-hydroxy phenyl) benzoxazole and derivative thereof, II, III are respectively a kind of in phenyl ring, naphthalene nucleus or the phenanthrene ring to 2-.
7. a kind of electroluminescent organic material according to claim 1 is characterized in that, the two tooth parts at I place are 2-(2-hydroxy phenyl) benzoglyoxaline and derivative thereof, and II, III are respectively a kind of in phenyl ring, naphthalene nucleus or the phenanthrene ring.
8. a kind of electroluminescent organic material according to claim 1 is characterized in that, the two tooth parts at wherein said I place are 2-(2-hydroxy phenyl) benzothiazole and derivative thereof, and II, III are respectively a kind of in phenyl ring, naphthalene nucleus or the phenanthrene ring.
9. a kind of electroluminescent organic material according to claim 1 is characterized in that, wherein the two tooth parts at I place are 10-hydroxy benzo quinoline, and II, III are respectively a kind of in phenyl ring, naphthalene nucleus or the phenanthrene ring.
10. a kind of electroluminescent organic material according to claim 1 is characterized in that, wherein the two tooth parts at I place are pyridine-2-formic acid, and II, III are phenyl ring.
11. the application of the described a kind of electroluminescent organic material of claim 1, it is characterized in that this material can be used on carrier blocking layers or the luminescent layer in the organic electroluminescence device of being made up of the multilayer organic materials, also can be used as adulterated dyestuff or as the bulk material of red dye.
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| KR100994083B1 (en) | 2003-07-31 | 2010-11-12 | 미쓰비시 가가꾸 가부시키가이샤 | Compound, charge transport material and organic electroluminescent device |
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| KR101131118B1 (en) * | 2003-12-02 | 2012-04-03 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Organic metal complex and light-emitting device using same |
| CN100344958C (en) * | 2005-02-18 | 2007-10-24 | 陕西师范大学 | Method for preparing fluovescence sensing film of densitive to compound containing nitroaromatics |
| CN101891895B (en) * | 2010-07-28 | 2011-11-30 | 南京航空航天大学 | Benzothiazole derivatives metal coordination polymer based on bridged bis-salicylaldehyde structure as well as manufacture method and application thereof |
| TWI564294B (en) | 2015-08-24 | 2017-01-01 | 國立清華大學 | Carrier generation material and organic light emitting diode |
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