CN103965876A - Green-yellow light-emitting organic electroluminescent material, its preparation method and organic electroluminescent device - Google Patents
Green-yellow light-emitting organic electroluminescent material, its preparation method and organic electroluminescent device Download PDFInfo
- Publication number
- CN103965876A CN103965876A CN201310036250.6A CN201310036250A CN103965876A CN 103965876 A CN103965876 A CN 103965876A CN 201310036250 A CN201310036250 A CN 201310036250A CN 103965876 A CN103965876 A CN 103965876A
- Authority
- CN
- China
- Prior art keywords
- reaction
- green light
- yellow green
- organic material
- compd
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The invention belongs to the field of organic electroluminescent materials and discloses a green-yellow light-emitting organic electroluminescent material, its preparation method and an organic electroluminescent device. The green-yellow light-emitting organic electroluminescent material has a structure shown in the formula and in the formula, R represents alkyl or alkoxy. The green-yellow light-emitting organic electroluminescent material comprises 2-phenylbenzothiazole as a ring metal ligand main structure, also comprises 2,2,6,6-tetramethyl-3,5-heptanedione as an auxiliary ligand and also comprises an alkyl chain or an alkoxy chain on the phenyl of the ring metal ligand so that material luminescence color adjustment is realized and emission of phosphorescent lights having different green-yellow light wavelengths is realized.
Description
Technical field
The present invention relates to field of organic electroluminescent materials, relate in particular to a kind of yellow green light electroluminescent organic material and preparation method thereof.The invention still further relates to a kind of organic electroluminescence device of this yellow green light electroluminescent organic material as the doping guest materials of luminescent layer that use.
Background technology
Organic electroluminescent refers to that organic materials is under electric field action, electric energy is converted into a kind of luminescence phenomenon of luminous energy.In early days former because the driving voltage of organic electroluminescence device is too high, luminous efficiency is very low etc. thereby make the research of organic electroluminescent stay cool.Until 1987, the human hairs such as the Tang of Kodak understand with oxine aluminium (Alq
3) be luminescent material, make the high-quality thin film of even compact with aromatic diamine, make low-work voltage, high brightness, high efficiency organic electroluminescence device, open the new prelude to electroluminescent organic material research.But due to the restriction of the statistical theory that is subject to spinning, the theoretical internal quantum efficiency limit of fluorescent material is only 25%, how makes full use of all the other phosphorescence of 75% and realize higher luminous efficiency and become the hot research direction in this field after this.1997, Forrest etc. found electrophosphorescence phenomenon, and the internal quantum efficiency of electroluminescent organic material has been broken through 25% restriction, makes the research of electroluminescent organic material enter another new period.
In research subsequently, the title complex of small molecules doping type transition metal has become people's research emphasis, as the title complex of iridium, ruthenium, platinum etc.The advantage of this class title complex is that they can obtain very high emitted energy from the triplet state of self, and metal iridium (III) compound wherein, due to good stability, reaction conditions gentleness in building-up process, and there is very high electroluminescent properties, in research process subsequently, accounting for dominant position always.
In order to make device obtain full-color demonstration, generally must obtain ruddiness, green glow and the blue light material of excellent performance simultaneously.And gold-tinted is middle shade, originally in the time forming white light OLED, used less than, but outside red, green, blue three primary colours, add again yellow, can increase the saturation ratio of white light.The gold-tinted phosphor material being in the news is the earliest (bt) of Thompson and the development of Forrest research team
2ir (acac) (two (2-phenyl benzothiazole-N, C
2') (methyl ethyl diketone) close iridium).Because gold-tinted is non-essential photochromic in three primary colours, it is also few to be deliberately engaged in the research of yellow phosphorescence developing material.So can grow the research field of phosphorescent light-emitting materials concerning the research in a sense of yellow phosphorescence material.
Summary of the invention
Based on the problems referred to above, problem to be solved by this invention is to provide a kind of yellow green light electroluminescent organic material.
Technical scheme of the present invention is as follows:
A kind of yellow green light electroluminescent organic material, its structural formula is as follows:
In formula, R is alkyl or alkoxyl group.
Described yellow green light electroluminescent organic material, wherein, R is C
1~ C
4alkyl or C
1~ C
4alkoxyl group.
The present invention also provides a kind of preparation method of above-mentioned yellow green light electroluminescent organic material, comprises the steps:
The following compd A of structural formula and compd B are provided:
A:
b:
in compd B, R is alkyl or alkoxyl group;
Under protection of inert gas, compd A, compd B and rake catalyzer are dissolved in solvent, in solvent, add sodium carbonate or salt of wormwood subsequently; be heated to reflux state, stirring reaction 6 ~ 15h, naturally cools to room temperature; separating-purifying reaction solution, obtains structural formula and is
compound C; Wherein, the mol ratio of compd A and compd B is 1:1.2; The mole dosage of sodium carbonate or salt of wormwood is 3 times of compd A; Described solvent is that volume ratio is the toluene of 3:1 and mixed solvent, tetrahydrofuran (THF), DMF or the toluene of ethanol composition; Described rake catalyzer is tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride, 0.01 ~ 0.05 times of the molar weight that the molar weight of described rake catalyzer is compd A;
Under protection of inert gas, three hydration iridous chlorides and described Compound C are dissolved in to back flow reaction 24h in the mixed solvent of cellosolvo and water, are cooled to room temperature, separating-purifying reaction solution, obtains structural formula and is
compound D; Wherein, the mol ratio of three hydration iridous chlorides and Compound C is 1:2.2; The volume ratio of cellosolvo and water is 4:1;
Under protection of inert gas, by described Compound D and structural formula be
2,2,6,6-tetramethyl--3,5-heptadione is at 1,2-ethylene dichloride, methylene dichloride, trichloromethane, in cellosolvo solvent, back flow reaction 8 ~ 20h, is cooled to room temperature, separating-purifying reaction solution obtains structural formula and is
yellow green light electroluminescent organic material; Wherein, the mol ratio of Compound D and methyl ethyl diketone is 1:2.
The preparation method of described yellow green light electroluminescent organic material, wherein, R is C
1~ C
4alkyl or C
1~ C
4alkoxyl group.
The preparation method of described yellow green light electroluminescent organic material, wherein, the separating-purifying of described Compound C comprises following process:
After reaction stops, being chilled to after room temperature, in reaction solution, adding distilled water, toluene extracts and merges after organic phase subsequently, washing, anhydrous MgSO
4dry organic phase; Clean, filter organic phase, after filtrate decompression is steamed and desolventized, the normal hexane taking volume ratio as 1:1 separates as elutriant carries out silica gel column chromatography with methylene dichloride mixed solution, obtains Compound C described in solid.
The preparation method of described yellow green light electroluminescent organic material, wherein, the separating-purifying of described Compound D comprises following process:
Stopped reaction is chilled to after room temperature, in reaction solution, drips distilled water, has Precipitation in reaction mixture, filter, and the throw out methanol wash that filtration is obtained, obtain described Compound D.
The preparation method of described yellow green light electroluminescent organic material, wherein, the separating-purifying of described yellow green light electroluminescent organic material comprises following process:
Reaction stops being chilled to after room temperature, and rotation is steamed and desolventized, and methanol wash crude product, carries out silica gel column chromatography separation taking methylene dichloride as elutriant to crude product subsequently, final described yellow green light electroluminescent organic material.
The present invention also provides a kind of organic electroluminescence device, and the material of its luminescent layer is that doping guest materials is doped to N according to the massfraction of 8wt%, two carbazyl-4 of N'-, the doping mixing material of 4'-dipyridyl composition; The structural formula of described doping guest materials is as follows:
In formula, R is alkyl or alkoxyl group.
Described organic electroluminescence device, wherein, R is C
1~ C
4alkyl or C
1~ C
4alkoxyl group.
Yellow green light electroluminescent organic material provided by the invention, taking 2-phenyl benzothiazole as cyclic metal complexes agent structure, with 2,2,6,6-tetramethyl--3,5-heptadione is assistant ligand, and on cyclic metal complexes, on phenyl, introduce alkyl chain or oxyalkyl chain, realize the adjusting to material glow color, thereby obtain the phosphorescent emissions of different yellow-green colour emission wavelengths.
Brief description of the drawings
Fig. 1 is the emmission spectrum of the yellow green light electroluminescent organic material that makes of embodiment 1;
Fig. 2 is the structural representation of the organic electroluminescence device that makes of embodiment 9.
Embodiment
The invention reside in and select taking 2-phenyl benzothiazole as cyclic metal complexes agent structure, taking methyl ethyl diketone as assistant ligand, synthetic a kind of green glow organic electromechanical phosphorescent material iridium metal complex, and the method for chemically modified by introducing alkyl chain or oxyalkyl chain on phenyl on cyclic metal complexes realizes the adjusting to material glow color, thereby obtain the phosphorescent emissions of different green emitting wavelength.
Green glow organic electromechanical phosphorescent material provided by the invention, general structure is as follows:
Wherein, R is alkyl or is alkoxyl group; Preferably, R is C
1~ C
4alkyl or C
1~ C
4alkoxyl group, comprise straight chain and various side chain.
The cyclic metal complexes of green glow organic electromechanical phosphorescent material iridium metal complex can be following structure:
This type of green glow organic electromechanical phosphorescent material metal iridium complex of the present invention can be used as the luminescent material in yellow green light or white light organic electroluminescent device.
The feature of this class green glow organic electromechanical phosphorescent material metal iridium complex provided by the invention is taking 2-phenyl benzothiazole as cyclic metal complexes agent structure, and the alkyl of different straight chains or straight chain, the introducing of alkoxyl group can obtain and be satisfied with yellow green light emission wavelength.
The preparation method of above-mentioned yellow green light electroluminescent organic material provided by the invention, comprises the steps:
Under S1, rare gas element (nitrogen, argon gas at least one, lower with) protection, by structural formula be
compd A (2-bromobenzene thiophthene), structural formula be
compd B (4-alkylbenzene boric acid or 4-alkoxy benzene boric acid) and rake catalyzer be dissolved in solvent, in solvent, add sodium carbonate or salt of wormwood subsequently, be heated to reflux state, stirring reaction 6 ~ 15h, naturally cool to room temperature, separating-purifying reaction solution, obtains structural formula and is
compound C (2-(4 '-alkyl phenyl) benzothiazole or 2-(4 '-alkoxyl phenyl) benzothiazole); Wherein, the mol ratio of compd A and compd B is 1:1.2; The mole dosage of sodium carbonate or salt of wormwood is 3 times of compd A; Described rake catalyzer is tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride, 0.01 ~ 0.05 times of the molar weight that the molar weight of described rake catalyzer is compd A; Reaction formula is as follows:
r is alkyl or alkoxyl group;
Under S2, protection of inert gas, by three hydration iridous chloride (IrCl
33H
2o) be dissolved in back flow reaction 24h in the mixed solvent of cellosolvo and water with described Compound C, be cooled to room temperature, separating-purifying reaction solution, obtains structural formula and is
compound D (2-(4 '-alkyl phenyl) benzothiazole containing iridium dichloro dimer or 2-(4 '-alkoxyl phenyl) benzothiazole containing iridium dichloro dimer); Wherein, the mol ratio of three hydration iridous chlorides and Compound C is 1:2.2; The volume ratio of cellosolvo and water is 4:1; Reaction formula is as follows:
Under S3, protection of inert gas, by described Compound D and structural formula be
2,2,6,6-tetramethyl--3,5-heptadione is back flow reaction 8 ~ 20h in 1,2-ethylene dichloride, methylene dichloride, trichloromethane, cellosolvo solvent, is cooled to room temperature, separating-purifying reaction solution obtains structural formula and is
yellow green light electroluminescent organic material; Wherein, the mol ratio of Compound D and methyl ethyl diketone is 1:2; Reaction formula is as follows:
The preparation method of above-mentioned yellow green light electroluminescent organic material, in step S1, R is C
1~ C
4alkyl or C
1~ C
4alkoxyl group, comprise straight chain and various side chain.
The preparation method of above-mentioned yellow green light electroluminescent organic material, in step S1, the separating-purifying of described Compound C comprises following process:
After reaction stops, being chilled to after room temperature, in reaction solution, adding distilled water, toluene extracts and merges after organic phase subsequently, washing, anhydrous MgSO
4dry organic phase; Clean, filter organic phase, after filtrate decompression is steamed and desolventized, taking volume ratio as the normal hexane of 1: 1 separates as elutriant carries out silica gel column chromatography with methylene dichloride mixed solution, obtain Compound C described in solid.
The preparation method of above-mentioned yellow green light electroluminescent organic material, in step S2, the separating-purifying of described Compound D comprises following process:
Stopped reaction is chilled to after room temperature, in reaction solution, drips distilled water, has Precipitation in reaction mixture, filter, and the throw out methanol wash that filtration is obtained, obtain described Compound D.
The preparation method of above-mentioned yellow green light electroluminescent organic material, in step S3, the separating-purifying of described yellow green light electroluminescent organic material comprises following process:
Reaction stops being chilled to after room temperature, and rotation is steamed and desolventized, and methanol wash crude product, carries out silica gel column chromatography separation taking methylene dichloride as elutriant to crude product subsequently, final described yellow green light electroluminescent organic material.
The preparation method of above-mentioned smooth electroluminescent organic material, adopts the benzothiazole ring with bromine atoms first with substituent phenylo boric acid generation Suzuki linked reaction to generate cyclic metal complexes 2-(4'-substituting group phenyl) benzothiazole.Cyclic metal complexes and IrCl
33H
2what O reaction generation was corresponding contains iridium chlorine bridge dipolymer, last and assistant ligand 2,2,6, and 6-tetramethyl--3, the reaction of 5-heptadione makes target iridium metal complex.
In addition, the present invention also provides a kind of green glow organic electromechanical phosphorescent material metal iridium complex organic electroluminescence device.
A kind of organic electroluminescence device, the material of its luminescent layer is that doping guest materials is doped to N according to the massfraction of 8wt%, two carbazyl-4 of N'-, the doping mixing material of 4'-dipyridyl composition; The structural formula of described doping guest materials is as follows:
Wherein, R is alkyl or is alkoxyl group; Preferably, R is C
1~ C
4alkyl or C
1~ C
4alkoxyl group, comprise straight chain and various side chain.
Above-mentioned yellow green light electroluminescent organic material, has good consistency with the material of main part in organic electroluminescence device luminescent layer, can be widely used in and prepare green glow or white-light phosphor photoelectricity electroluminescence device.Electroluminescent device, owing to containing the yellow green light organic electromechanical phosphorescent material metal iridium complex of high color purity in luminescent layer, can be launched high purity yellow green light and good device performance thereby it has advantages of.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1: title complex two (2-(4 '-aminomethyl phenyl) benzothiazole-N, C
2') (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium
(1) 2-(4 '-aminomethyl phenyl) benzothiazole is synthetic
Under nitrogen protection, by (2.14g, 0.01mol) 2-bromobenzene thiophthene, (1.63g, 0.012mol) 4-toluene boric acid and (0.35g, 0.0003mol) Pd (PPh
3)
4be dissolved in the mixing solutions being made up of 15mL toluene and 5ml ethanol, adding 15mL concentration is the Na of 2M
2cO
3the aqueous solution, is heated to reflux state, stirring reaction 10h.Naturally be chilled to after room temperature, add appropriate distilled water, toluene extraction.Merge after organic phase washing, anhydrous MgSO
4dry organic phase.Filter, after filtrate decompression is steamed and desolventized, the normal hexane taking volume ratio as 1:1 separates as elutriant carries out silica gel column chromatography with methylene dichloride mixed solution, obtains solid 1.58g, and yield is 70.1%.Reaction equation is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 225.1 (M
++ 1)
Ultimate analysis: C
14h
11nS
Theoretical value: C, 74.63; H, 4.92; N, 6.22; S, 14.23;
Measured value: C, 74.60; H, 4.95; N, 6.25; S, 14.20.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(4 '-aminomethyl phenyl) benzothiazole.
(2) cyclic metal complexes is the dimeric synthetic containing iridium dichloro of 2-(4 '-aminomethyl phenyl) benzothiazole
Under nitrogen protection, (0.70g, 2mmol) IrCl
33H
2o tri-hydration iridous chlorides and (0.99g, 4.4mmol) 2-(4 '-aminomethyl phenyl) benzothiazole back flow reaction 24h in the mixed solvent of 40ml2-ethoxy ethanol and 10mL water.Be chilled to after room temperature, drip appropriate distilled water, in reaction mixture, have Precipitation.Filter throw out methanol wash.Making dimer need not further purify, and can be directly used in next step reaction.Reaction equation is as follows:
(3) two (2-(4 '-aminomethyl phenyl) benzothiazole-N, C of title complex
2') (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium
Under nitrogen protection, the above-mentioned dimer making and 1mL2,2,6,6-tetramethyl--3,5-heptadione is at 30mL1, back flow reaction 20h in 2-ethylene dichloride solvent.Be chilled to after room temperature, rotation is steamed and is desolventized, methanol wash crude product.Taking methylene dichloride as elutriant, crude product is carried out to silica gel column chromatography separation, the final pure substance 0.25g that obtains, yield is 30.3%.Reaction equation is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 824.2 (M
++ 1)
Ultimate analysis: C
39h
39irN
2o
2s
2
Theoretical value: C, 56.84; H, 4.77; Ir, 23.32; N, 3.40; O, 3.88; S, 7.78;
Measured value: C, 56.76; H, 4.83; Ir, 23.37; N, 3.42; O, 3.83; S, 7.79.
The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4 '-aminomethyl phenyl) benzothiazole-N, C of title complex
2') (2,2,6,6-tetramethyl--3,5-heptadione) close iridium.
As shown in Figure 1, transverse axis is emission wavelength (nm of unit), and the longitudinal axis is the photoluminescence intensity after normalization method, and end product is at 298K temperature Toluene solution (~ 10
-5the maximum emission peak of middle emmission spectrum M) is at 555nm place, can be used as yellow green light electroluminescent material and be widely used in the preparation field of organic electroluminescence device.
In addition, 10
-5the CH of M end product
2cl
2solution is at 298K temperature, with the fac-Ir under the same terms (ppy)
3toluene solution be standard (Φ
pl=0.40), record the Φ of end product
pl=0.31, the iridium electroluminescent organic material that contains of visible the present embodiment has higher internal quantum efficiency and electroluminescent efficiency.
Embodiment 2: title complex two (2-(4 '-ethylphenyl) benzothiazole-N, C
2') (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium
(1) 2-(4 '-ethylphenyl) benzothiazole is synthetic
Under nitrogen protection, by (2.14g, 0.01mol) 2-bromobenzene thiophthene, (1.80g, 0.012mol) 4-ethylbenzene boric acid and (0.35g, 0.0003mol) Pd (PPh
3)
4be dissolved in by 20mL THF, adding 15mL concentration is the Na of 2M
2cO
3the aqueous solution, is heated to reflux state, stirring reaction 15h.Naturally be chilled to after room temperature, add appropriate distilled water, toluene extraction.Merge after organic phase washing, anhydrous MgSO
4dry organic phase.Filter, after filtrate decompression is steamed and desolventized, the normal hexane taking volume ratio as 2:1 separates as elutriant carries out silica gel column chromatography with methylene dichloride mixed solution, obtains solid 1.44g, and yield is 60.2%.Reaction equation is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 239.1 (M
++ 1)
Ultimate analysis: C
15h
13nS
Theoretical value: C, 75.28; H, 5.47; N, 5.85; S, 13.40;
Measured value: C, 75.25; H, 5.45; N, 5.87; S, 13.43.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(4 '-ethylphenyl) benzothiazole.
(2) part is the dimeric synthetic containing iridium dichloro of 2-(4 '-ethylphenyl) benzothiazole
Under nitrogen protection, (0.70g, 2mmol) IrCl
33H
2o tri-hydration iridous chlorides and (1.05g, 4.4mmol) 2-(4 '-ethylphenyl) benzothiazole back flow reaction 24h in the mixed solvent of 40ml2-ethoxy ethanol and 10mL water.Be chilled to after room temperature, drip appropriate distilled water, in reaction mixture, have Precipitation.Filter throw out methanol wash.The dimer making need not further be purified, and can be directly used in next step reaction.Reaction equation is as follows:
(3) two (2-(4 '-ethylphenyl) benzothiazole-N, C of title complex
2') (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium
Under nitrogen protection, by the above-mentioned dimer making and 1mL2,2,6,6-tetramethyl--3,5-heptadione is back flow reaction 20h in 30mL dichloromethane solvent.Be chilled to after room temperature, rotation is steamed and is desolventized, methanol wash crude product.Taking methylene dichloride as elutriant, crude product is carried out to silica gel column chromatography separation, the final pure substance 0.21g that obtains, yield is 24.6%.Reaction equation is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 852.2 (M
++ 1)
Ultimate analysis: C
41h
43irN
2o
2s
2
Theoretical value: C, 57.79; H, 5.09; Ir, 22.56; N, 3.29; O, 3.76; S, 7.53;
Measured value: C, 57.72; H, 5.13; Ir, 22.59; N, 3.22; O, 3.77; S, 7.57.
The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4 '-ethylphenyl) benzothiazole-N, C of title complex
2') (2,2,6,6-tetramethyl--3,5-heptadione) close iridium.
End product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of middle emmission spectrum M) is at 552nm place.In addition, 10
-5the toluene solution of M end product is at 298K temperature, with the fac-Ir under the same terms (ppy)
3toluene solution be standard (Φ
pl=0.40), record the Φ of end product
pl=0.22.
Embodiment 3: title complex two (2-(4 '-n-propyl phenyl) benzothiazole-N, C
2') (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium
(1) 2-(4 '-n-propyl phenyl) benzothiazole is synthetic
Under nitrogen protection; by (2.14g; 0.01mol) 2-bromobenzene thiophthene; (1.97g; 0.012mol) 4-n-propylbenzene boric acid and (0.21g; 0.0003mol) dichloro bi triphenyl phosphine palladium is dissolved in by 20mL N,N-dimethylacetamide, and adding 15mL concentration is the Na of 2M
2cO
3the aqueous solution, is heated to reflux state, stirring reaction 10h.Naturally be chilled to after room temperature, add appropriate distilled water, toluene extraction.Merge after organic phase washing, anhydrous MgSO
4dry organic phase.Filter, after filtrate decompression is steamed and desolventized, the normal hexane taking volume ratio as 1:1 separates as elutriant carries out silica gel column chromatography with methylene dichloride mixed solution, obtains solid 1.42g, and yield is 56.0%.Reaction equation is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 253.1 (M
++ 1)
Ultimate analysis: C
16h
15nS
Theoretical value: C, 75.85; H, 5.97; N, 5.53; S, 12.66;
Measured value: C, 75.81; H, 5.99; N, 5.54; S, 12.67.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(4 '-n-propyl phenyl) benzothiazole.
(2) part is the dimeric synthetic containing iridium dichloro of 2-(4 '-n-propyl phenyl) benzothiazole
Under nitrogen protection, (0.70g, 2mmol) IrCl
33H
2o tri-hydration iridous chlorides and (1.11g, 4.4mmol) 2-(4 '-n-propyl phenyl) benzothiazole back flow reaction 24h in the mixed solvent of 40ml2-ethoxy ethanol and 10mL water.Be chilled to after room temperature, drip appropriate distilled water, in reaction mixture, have Precipitation.Filter throw out methanol wash.The dimer making need not further be purified, and can be directly used in next step reaction.Reaction equation is as follows:
(3) two (2-(4 '-n-propyl phenyl) benzothiazole-N, C of title complex
2') (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium
Under nitrogen protection, the above-mentioned dimer making and 1mL2,2,6,6-tetramethyl--3,5-heptadione is back flow reaction 16h in 50mL trichloromethane solvent.Be chilled to after room temperature, rotation is steamed and is desolventized, methanol wash crude product.Taking methylene dichloride as elutriant, crude product is carried out to silica gel column chromatography separation, the final pure substance 0.22g that obtains, yield is 25.0%.Reaction equation is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 796.2 (M
++ 1)
Ultimate analysis: C
43h
47irN
2o
2s
2
Theoretical value: C, 58.68; H, 5.38; Ir, 21.84; N, 3.18; O, 3.64; S, 7.29;
Measured value: C, 58.64; H, 5.32; Ir, 21.91; N, 3.19; O, 3.67; S, 7.28.
The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4 '-n-propyl phenyl) benzothiazole-N, C of title complex
2') (2,2,6,6-tetramethyl--3,5-heptadione) close iridium.
End product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of middle emmission spectrum M) is at 550nm place.In addition, 10
-5the toluene solution of M end product is at 298K temperature, with the fac-Ir under the same terms (ppy)
3toluene solution be standard (Φ
pl=0.40), record the Φ of end product
pl=0.13.
Embodiment 4: title complex two (2-(4 '-tert-butyl-phenyl) benzothiazole-N, C
2') (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium
(1) 2-(4 '-tert-butyl-phenyl) benzothiazole is synthetic
Under nitrogen protection, by (2.14g, 0.01mol) 2-bromobenzene thiophthene, (2.14g, 0.012mol) 4-tert.-butylbenzene boric acid and (0.35g, 0.0003mol) Pd (PPh
3)
4be dissolved in by 20mL toluene, adding 15mL concentration is the Na of 2M
2cO
3the aqueous solution, is heated to reflux state, stirring reaction 10h.Naturally be chilled to after room temperature, add appropriate distilled water, toluene extraction.Merge after organic phase washing, anhydrous MgSO
4dry organic phase.Filter, after filtrate decompression is steamed and desolventized, the normal hexane taking volume ratio as 3:1 separates as elutriant carries out silica gel column chromatography with methylene dichloride mixed solution, obtains solid 1.47g, and yield is 55.0%.Reaction equation is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 267.1 (M
++ 1)
Ultimate analysis: C
17h
17nS
Theoretical value: C, 76.36; H, 6.41; N, 5.24; S, 11.99;
Measured value: C, 76.33; H, 6.43; N, 5.26; S, 11.98.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(4 '-tert-butyl-phenyl) benzothiazole.
(2) part is the dimeric synthetic containing iridium dichloro of 2-(4 '-tert-butyl-phenyl) benzothiazole
Under nitrogen protection, (0.70g, 2mmol) IrCl
33H
2o tri-hydration iridous chlorides and (1.18g, 4.4mmol) 2-(4 '-tert-butyl-phenyl) benzothiazole back flow reaction 24h in the mixed solvent of 40ml2-ethoxy ethanol and 10mL water.Be chilled to after room temperature, drip appropriate distilled water, in reaction mixture, have Precipitation.Filter throw out methanol wash.The dimer making need not further be purified, and can be directly used in next step reaction.Reaction equation is as follows:
(3) two (2-(4 '-tert-butyl-phenyl) benzothiazole-N, C of title complex
2') (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium
Under nitrogen protection, the above-mentioned dimer making and 1mL2,2,6,6-tetramethyl--3,5-heptadione is back flow reaction 6h in 30mL2-ethoxy ethanol solvent.Be chilled to after room temperature, rotation is steamed and is desolventized, methanol wash crude product.Taking methylene dichloride as elutriant, crude product is carried out to silica gel column chromatography separation, the final pure substance 0.20g that obtains, yield is 22.0%.Reaction equation is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 824.2 (M
++ 1)
Ultimate analysis: C
45h
51irN
2o
2s
2
Theoretical value: C, 59.51; H, 5.66; Ir, 21.16; N, 3.08; O, 3.52; S, 7.06;
Measured value: C, 59.58; H, 5.62; Ir, 21.14; N, 3.02; O, 3.56; S, 7.08.
The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4 '-tert-butyl-phenyl) benzothiazole-N, C of title complex
2') (2,2,6,6-tetramethyl--3,5-heptadione) close iridium.
End product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of middle emmission spectrum M) is at 551nm place.In addition, 10
-5the toluene solution of M end product is at 298K temperature, with the fac-Ir under the same terms (ppy)
3toluene solution be standard (Φ
pl=0.40), record the Φ of end product
pl=0.21.
Embodiment 5: title complex two (2-(4 '-p-methoxy-phenyl) benzothiazole-N, C
2') (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium
(1) 2-(4 '-p-methoxy-phenyl) benzothiazole is synthetic
Under nitrogen protection; by (2.14g; 0.01mol) 2-bromobenzene thiophthene; (1.82g; 0.012mol) 4-methoxyphenylboronic acid and (0.28g; 0.0004mol) dichloro bi triphenyl phosphine palladium is dissolved in the mixing solutions being made up of 15mL toluene and 5ml ethanol, and adding 15mL concentration is the K of 2M
2cO
3the aqueous solution, is heated to reflux state, stirring reaction 10h.Naturally be chilled to after room temperature, add appropriate distilled water, toluene extraction.Merge after organic phase washing, anhydrous MgSO
4dry organic phase.Filter, after filtrate decompression is steamed and desolventized, the normal hexane taking volume ratio as 3:1 separates as elutriant carries out silica gel column chromatography with methylene dichloride mixed solution, obtains solid 1.56g, and yield is 64.6%.Reaction equation is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 241.1 (M
++ 1)
Ultimate analysis: C14H11NOS
Theoretical value: C, 69.68; H, 4.59; N, 5.80; O, 6.63; S, 13.29;
Measured value: C, 69.62; H, 4.57; N, 5.85; O, 6.64; S, 13.31.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(4 '-p-methoxy-phenyl) benzothiazole.
(2) cyclic metal complexes is the dimeric synthetic containing iridium dichloro of 2-(4 '-p-methoxy-phenyl) benzothiazole
Under nitrogen protection, (0.70g, 2mmol) IrCl
33H
2o tri-hydration iridous chlorides and (1.06g, 4.4mmol) 2-(4 '-aminomethyl phenyl) benzothiazole back flow reaction 24h in the mixed solvent of 30ml2-ethoxy ethanol and 10mL water.Be chilled to after room temperature, drip appropriate distilled water, in reaction mixture, have Precipitation.Filter throw out methanol wash.The dimer making need not further be purified, and can be directly used in next step reaction.Reaction equation is as follows:
(3) title complex two (2-(4 '-p-methoxy-phenyl) benzothiazole-N, C
2') (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium
Under nitrogen protection, the above-mentioned dimer making and (0.15g, 1.5mmol) 2,2,6,6-tetramethyl--3,5-heptadione is at 30mL1, back flow reaction 20h in 2-ethylene dichloride solvent.Be chilled to after room temperature, rotation is steamed and is desolventized, methanol wash crude product.Taking methylene dichloride as elutriant, crude product is carried out to silica gel column chromatography separation, the final pure substance 0.24g that obtains, yield is 28.0%.Reaction equation is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 856.2 (M
++ 1)
Ultimate analysis: C
39h
39irN
2o
4s
2
Theoretical value: C, 54.72; H, 4.59; Ir, 22.45; N, 3.27; O, 7.48; S, 7.49;
Measured value: C, 54.66; H, 4.63; Ir, 22.41; N, 3.33; O, 7.44; S, 7.53.
The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4 '-p-methoxy-phenyl) benzothiazole-N, C of title complex
2') (2,2,6,6-tetramethyl--3,5-heptadione) close iridium
End product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of middle emmission spectrum M) is at 553nm place.In addition, 10
-5the toluene solution of M end product is at 298K temperature, with the fac-Ir under the same terms (ppy)
3toluene solution be standard (Φ
pl=0.40), record the Φ of end product
pl=0.13.
Embodiment 6: title complex two (2-(4 '-ethoxyl phenenyl) benzothiazole-N, C
2') (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium
(1) 2-(4 '-ethoxyl phenenyl) benzothiazole is synthetic
Under nitrogen protection, by (2.14g, 0.01mol) 2-bromobenzene thiophthene, (1.99g, 0.012mol) 4-ethylbenzene boric acid and (0.58g, 0.0005mol) Pd (PPh
3)
4be dissolved in by 30mL THF, adding 15mL concentration is the K of 2M
2cO
3the aqueous solution, is heated to reflux state, stirring reaction 15h.Naturally be chilled to after room temperature, add appropriate distilled water, toluene extraction.Merge after organic phase washing, anhydrous MgSO
4dry organic phase.Filter, after filtrate decompression is steamed and desolventized, the normal hexane taking volume ratio as 3:1 separates as elutriant carries out silica gel column chromatography with methylene dichloride mixed solution, obtains solid 1.51g, and yield is 59.1%.Reaction equation is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 255.1 (M
++ 1)
Ultimate analysis: C
15h
13nOS
Theoretical value: C, 70.56; H, 5.13; N, 5.49; O, 6.27; S, 12.56;
Measured value: C, 70.50; H, 5.17; N, 5.55; O, 6.22; S, 12.56.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(4 '-ethoxyl phenenyl) benzothiazole
(2) part is the dimeric synthetic containing iridium dichloro of 2-(4 '-ethoxyl phenenyl) benzothiazole
Under nitrogen protection, (0.70g, 2mmol) IrCl
33H
2o tri-hydration iridous chlorides and (1.12g, 4.4mmol) 2-(4 '-ethoxyl phenenyl) benzothiazole back flow reaction 24h in the mixed solvent of 45ml2-ethoxy ethanol and 15mL water.Be chilled to after room temperature, drip appropriate distilled water, in reaction mixture, have Precipitation.Filter throw out methanol wash.Making dimer need not further purify, and can be directly used in next step reaction.Reaction equation is as follows:
(3) two (2-(4 '-ethoxyl phenenyl) benzothiazole-N, C of title complex
2') (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium
Under nitrogen protection, the above-mentioned dimer making and (0.14g, 1.375mmol) 2,2,6,6-tetramethyl--3,5-heptadione is at 30mL1, back flow reaction 20h in 2-ethylene dichloride solvent.Be chilled to after room temperature, rotation is steamed and is desolventized, methanol wash crude product.Taking methylene dichloride as elutriant, crude product is carried out to silica gel column chromatography separation, final pure substance 0.19g, yield is 21.5%.Reaction equation is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 884.2 (M
++ 1)
Ultimate analysis: C
41h
43irN
2o
4s
2
Theoretical value: C, 55.70; H, 4.90; Ir, 21.74; N, 3.17; O, 7.24; S, 7.25;
Measured value: C, 55.64; H, 4.95; Ir, 21.77; N, 3.13; O, 7.25; S, 7.26.
The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4 '-ethoxyl phenenyl) benzothiazole-N, C of title complex
2') (2,2,6,6-tetramethyl--3,5-heptadione) close iridium
End product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of middle emmission spectrum M) is at 549nm place.In addition, 10
-5the toluene solution of M end product is at 298K temperature, with the fac-Ir under the same terms (ppy)
3toluene solution be standard (Φ
pl=0.40), record the Φ of end product
pl=0.11.
Embodiment 7: title complex two (2-(4 '-positive propoxy phenyl) benzothiazole-N, C
2') (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium
(1) 2-(4 '-positive propoxy phenyl) benzothiazole is synthetic
Under nitrogen protection, by (2.14g, 0.01mol) 2-bromobenzene thiophthene, (2.16g, 0.012mol) 4-positive propoxy phenylo boric acid and (0.46g, 0.0004mol) Pd (PPh
3)
4be dissolved in by 20mL DMF, adding 15mL concentration is the Na of 2M
2cO
3the aqueous solution, is heated to reflux state, stirring reaction 10h.Naturally be chilled to after room temperature, add appropriate distilled water, toluene extraction.Merge after organic phase washing, anhydrous MgSO
4dry organic phase.Filter, after filtrate decompression is steamed and desolventized, the normal hexane taking volume ratio as 4:1 separates as elutriant carries out silica gel column chromatography with methylene dichloride mixed solution, obtains solid 1.35g, and yield is 50.1%.Reaction equation is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 269.1 (M
++ 1)
Ultimate analysis: C
16h
15nOS
Theoretical value: C, 71.34; H, 5.61; N, 5.20; O, 5.94; S, 11.90;
Measured value: C, 71.26; H, 5.68; N, 5.25; O, 5.90; S, 11.91.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(4 '-positive propoxy phenyl) benzothiazole.
(2) part is the dimeric synthetic containing iridium dichloro of 2-(4 '-positive propoxy phenyl) benzothiazole
Under nitrogen protection, (0.70g, 2mmol) IrCl
33H
2o tri-hydration iridous chlorides and (1.19g, 4.4mmol) 2-(4 '-n-propyl phenyl) benzothiazole back flow reaction 24h in the mixed solvent of 30ml2-ethoxy ethanol and 10mL water.Be chilled to after room temperature, drip appropriate distilled water, in reaction mixture, have Precipitation.Filter throw out methanol wash.Making dimer need not further purify, and can be directly used in next step reaction.Reaction equation is as follows:
(3) two (2-(4 '-positive propoxy phenyl) benzothiazole-N, C of title complex
2') (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium
Under nitrogen protection, the above-mentioned dimer making and (0.11g, 1.125mmol) 2,2,6,6-tetramethyl--3,5-heptadione is back flow reaction 20h in 30mL trichloromethane solvent.Be chilled to after room temperature, rotation is steamed and is desolventized, methanol wash crude product.Taking methylene dichloride as elutriant, crude product is carried out to silica gel column chromatography separation, the final pure substance 0.16g that obtains, yield is 17.5%.Reaction equation is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 912.3 (M
++ 1)
Ultimate analysis: C
43h
47iN
2o
4s
2
Theoretical value: C, 56.62; H, 5.19; Ir, 21.07; N, 3.07; O, 7.02; S, 7.03;
Measured value: C, 56.57; H, 5.26; Ir, 21.03; N, 3.10; O, 7.10; S, 6.94.
The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4 '-positive propoxy phenyl) benzothiazole-N, C of title complex
2') (2,2,6,6-tetramethyl--3,5-heptadione) close iridium.
End product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of middle emmission spectrum M) is at 547nm place.In addition, 10
-5the toluene solution of M end product is at 298K temperature, with the fac-Ir under the same terms (ppy)
3toluene solution be standard (Φ
pl=0.40), record the Φ of end product
pl=0.09.
Embodiment 8: title complex two (2-(4 '-tert.-butoxy phenyl) benzothiazole-N, C
2') (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium
(1) 2-(4 '-tert.-butoxy phenyl) benzothiazole is synthetic
Under nitrogen protection, by (2.14g, 0.01mol) 2-bromobenzene thiophthene, (2.33g, 0.012mol) 4-tert.-butoxy phenylo boric acid and (0.35g, 0.0005mol) Pd (PPh
3)
2cl
2be dissolved in by 20mL DMF, adding 15mL concentration is the K of 2M
2cO
3the aqueous solution, is heated to reflux state, stirring reaction 10h.Naturally be chilled to after room temperature, add appropriate distilled water, toluene extraction.Merge after organic phase washing, anhydrous MgSO
4dry organic phase.Filter, after filtrate decompression is steamed and desolventized, the normal hexane taking volume ratio as 5:1 separates as elutriant carries out silica gel column chromatography with methylene dichloride mixed solution, obtains solid 1.53g, and yield is 54.0%.Reaction equation is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 283.1 (M
++ 1)
Ultimate analysis: C
17h
17nOS
Theoretical value: C, 72.05; H, 6.05; N, 4.94; O, 5.65; S, 11.31;
Measured value: C, 72.04; H, 6.00; N, 4.88; O, 5.63; S, 11.35.
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(4 '-tert.-butoxy phenyl) benzothiazole.
(2) part is the dimeric synthetic containing iridium dichloro of 2-(4 '-tert.-butoxy phenyl) benzothiazole
Under nitrogen protection, (0.70g, 2mmol) IrCl
33H
2o tri-hydration iridous chlorides and (1.25g, 4.4mmol) 2-(4 '-tert-butyl-phenyl) benzothiazole back flow reaction 24h in the mixed solvent of 30ml2-ethoxy ethanol and 10mL water.Be chilled to after room temperature, drip appropriate distilled water, in reaction mixture, have Precipitation.Filter throw out methanol wash.The dimer making need not further be purified, and can be directly used in next step reaction.Reaction equation is as follows:
(3) two (2-(4 '-tert-butyl-phenyl) benzothiazole-N, C of title complex
2') (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium
Under nitrogen protection, the above-mentioned dimer making and (0.13g, 1.25mmol) 2,2,6,6-tetramethyl--3,5-heptadione is back flow reaction 20h in 40mL dichloromethane solvent.Be chilled to after room temperature, rotation is steamed and is desolventized, methanol wash crude product.Taking methylene dichloride as elutriant, crude product is carried out to silica gel column chromatography separation, the final pure substance 0.14g that obtains, yield is 14.9%.Reaction equation is as follows:
It is as follows that product detects data:
Mass spectrum (m/z): 940.3 (M
++ 1)
Ultimate analysis: C
45h
51irN
2o
4s
2
Theoretical value: C, 57.48; H, 5.47; Ir, 20.44; N, 2.98; O, 6.81; S, 6.82;
Measured value: C, 57.41; H, 5.52; Ir, 20.47; N, 2.94; O, 6.85; S, 6.81.
The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(4 '-tert.-butoxy phenyl) benzothiazole-N, C of title complex
2') (2,2,6,6-tetramethyl--3,5-heptadione) close iridium.
End product is CH at 298K temperature
2cl
2solution (~ 10
-5the maximum emission peak of middle emmission spectrum M) is at 550nm place.In addition, 10
-5the toluene solution of M end product is at 298K temperature, with the fac-Ir under the same terms (ppy)
3toluene solution be standard (Φ
pl=0.40), record the Φ of end product
pl=0.19.
Embodiment 9
The present embodiment is organic electroluminescence device, two (2-(4 '-aminomethyl phenyl) benzothiazole-N, C that it makes with embodiment 1
2') (2,2,6,6-tetramethyl--3,5-heptadione) close iridium (representing using P1) as luminescent layer doping guest materials; As shown in Figure 2, the structure of organic electroluminescence device comprises the transparent anode 301, hole injection layer 302, hole transmission layer 303, luminescent layer 304, hole blocking layer 305, electron transfer layer 306, electronic injection buffer layer 307, the negative electrode 308 that stack gradually.
The preparation technology of this organic electroluminescence device:
On a glass-based plate, depositing a layer thickness is 100nm, square resistance is that the tin indium oxide (ITO) of 10 ~ 20 Ω/mouths is as transparent anode 301, on anode 301, prepare successively by vacuum evaporation the 2-TNATA(4 that a layer thickness is 60nm, 4', 4 " tri-(N-(naphthalene-2-yl)-N-phenyl amino) triphenylamine) hole-injecting material is as hole injection layer 302, a layer thickness is the NPB(N of 20nm, N '-bis-(1-naphthyl)-N, N '-phenylbenzene benzidine) hole mobile material is as hole transmission layer 303, a layer thickness is the CBP (N doped with 8wt%P1 of 30nm, two carbazyl-4 of N'-, 4'-dipyridyl) mixing and doping guest materials is as luminescent layer 304, the BCP(2 that vacuum evaporation a layer thickness is successively 10nm on this luminescent layer 305 again, 9-dimethyl-4, 7-phenylbenzene-phenanthrolene) material is as hole blocking layer 305, thickness is that the Alq3 (three (oxine) aluminium) of 20nm is as electron transfer layer 306, thickness is that the Liq of 2nm is as electronic injection buffer layer 307, finally on buffer layer, adopt the metal A l that vacuum plating techniques of deposition thickness is 100nm, as the negative electrode 308 of device.Therefore, the structure of this organic electroluminescence device can be also ITO/2-TNATA/NPB/BCP:P1/BCP/Alq3/Liq/Al; Wherein, BCP:P1 represents that P1 is doped in BCP, and slash "/" represents laminate structure.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (9)
1. a yellow green light electroluminescent organic material, is characterized in that, its structural formula is as follows:
In formula, R is alkyl or alkoxyl group.
2. yellow green light electroluminescent organic material according to claim 1, is characterized in that, R is C
1~ C
4alkyl or C
1~ C
4alkoxyl group.
3. a preparation method for yellow green light electroluminescent organic material, is characterized in that, comprises the steps:
The following compd A of structural formula and compd B are provided:
A:
b:
in compd B, R is alkyl or alkoxyl group;
Under protection of inert gas, compd A, compd B and rake catalyzer are dissolved in solvent, in solvent, add sodium carbonate or salt of wormwood subsequently; be heated to reflux state, stirring reaction 6 ~ 15h, naturally cools to room temperature; separating-purifying reaction solution, obtains structural formula and is
compound C; Wherein, the mol ratio of compd A and compd B is 1:1.2; The mole dosage of sodium carbonate or salt of wormwood is 3 times of compd A; Described solvent is that volume ratio is the toluene of 3:1 and mixed solvent, tetrahydrofuran (THF), DMF or the toluene of ethanol composition; Described rake catalyzer is tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride, 0.01 ~ 0.05 times of the molar weight that the molar weight of described rake catalyzer is compd A;
Under protection of inert gas, three hydration iridous chlorides and described Compound C are dissolved in to back flow reaction 24h in the mixed solvent of cellosolvo and water, are cooled to room temperature, separating-purifying reaction solution, obtains structural formula and is
compound D; Wherein, the mol ratio of three hydration iridous chlorides and Compound C is 1:2.2; The volume ratio of cellosolvo and water is 4:1;
Under protection of inert gas, by described Compound D and structural formula be
2,2,6,6-tetramethyl--3,5-heptadione is back flow reaction 8 ~ 20h h in 1,2-ethylene dichloride, trichloromethane, methylene dichloride or cellosolvo solvent, is cooled to room temperature, separating-purifying reaction solution obtains structural formula and is
yellow green light electroluminescent organic material; Wherein, the mol ratio of Compound D and methyl ethyl diketone is 1:2.
4. the preparation method of yellow green light electroluminescent organic material according to claim 3, is characterized in that, R is C
1~ C
4alkyl or C
1~ C
4alkoxyl group.
5. the preparation method of yellow green light electroluminescent organic material according to claim 3, is characterized in that, the separating-purifying of described Compound C comprises following process:
After reaction stops, being chilled to after room temperature, in reaction solution, adding distilled water, toluene extracts and merges after organic phase subsequently, washing, anhydrous MgSO
4dry organic phase; Clean, filter organic phase, after filtrate decompression is steamed and desolventized, taking volume ratio as the normal hexane of 1: 1 separates as elutriant carries out silica gel column chromatography with methylene dichloride mixed solution, obtain Compound C described in solid.
6. the preparation method of yellow green light electroluminescent organic material according to claim 3, is characterized in that, the separating-purifying of described Compound D comprises following process:
Stopped reaction is chilled to after room temperature, in reaction solution, drips distilled water, has Precipitation in reaction mixture, filter, and the throw out methanol wash that filtration is obtained, obtain described Compound D.
7. the preparation method of yellow green light electroluminescent organic material according to claim 3, is characterized in that, the separating-purifying of described yellow green light electroluminescent organic material comprises following process:
Reaction stops being chilled to after room temperature, and rotation is steamed and desolventized, and methanol wash crude product, carries out silica gel column chromatography separation taking methylene dichloride as elutriant to crude product subsequently, final described yellow green light electroluminescent organic material.
8. an organic electroluminescence device, is characterized in that, the material of its luminescent layer is that doping guest materials is doped to N according to the massfraction of 8wt%, two carbazyl-4 of N'-, the doping mixing material of 4'-dipyridyl composition; The structural formula of described doping guest materials is as follows:
In formula, R is alkyl or alkoxyl group.
9. organic electroluminescence device according to claim 8, is characterized in that, R is C
1~ C
4alkyl or C
1~ C
4alkoxyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310036250.6A CN103965876A (en) | 2013-01-30 | 2013-01-30 | Green-yellow light-emitting organic electroluminescent material, its preparation method and organic electroluminescent device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310036250.6A CN103965876A (en) | 2013-01-30 | 2013-01-30 | Green-yellow light-emitting organic electroluminescent material, its preparation method and organic electroluminescent device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103965876A true CN103965876A (en) | 2014-08-06 |
Family
ID=51235890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310036250.6A Pending CN103965876A (en) | 2013-01-30 | 2013-01-30 | Green-yellow light-emitting organic electroluminescent material, its preparation method and organic electroluminescent device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103965876A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106158416A (en) * | 2016-08-22 | 2016-11-23 | 电子科技大学 | A kind of Graphene/zinc oxide composite material of core-shell structure is the preparation method of the ultracapacitor of negative pole |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050176624A1 (en) * | 2003-08-07 | 2005-08-11 | Thompson Mark E. | Organometallic complexes as singlet oxygen sensitizers |
| CN101020821A (en) * | 2007-03-05 | 2007-08-22 | 四川大学 | Organic electrofluorescent iridium complex material |
| CN101607972A (en) * | 2008-06-17 | 2009-12-23 | 比亚迪股份有限公司 | Benzothiazole-complex of iridium and the organic electroluminescence device that uses this title complex |
-
2013
- 2013-01-30 CN CN201310036250.6A patent/CN103965876A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050176624A1 (en) * | 2003-08-07 | 2005-08-11 | Thompson Mark E. | Organometallic complexes as singlet oxygen sensitizers |
| CN101020821A (en) * | 2007-03-05 | 2007-08-22 | 四川大学 | Organic electrofluorescent iridium complex material |
| CN101607972A (en) * | 2008-06-17 | 2009-12-23 | 比亚迪股份有限公司 | Benzothiazole-complex of iridium and the organic electroluminescence device that uses this title complex |
Non-Patent Citations (4)
| Title |
|---|
| JAE-HO CHOI等: "Solution processable organic electro-phosphorescent iridium complex based on a benzothiazole derivative", 《SYNTHETIC METALS》, vol. 159, 21 May 2009 (2009-05-21), pages 1517 - 1521, XP026391488 * |
| LIANQING CHEN等: "Tuning of emission: Synthesis, structure and photophysical properties of imidazole, oxazole and thiazole-based iridium (III) complexes", 《INORGANICA CHIMICA ACTA》, vol. 359, 30 June 2006 (2006-06-30), pages 4207 - 4214 * |
| WEI-CHIEH CHANG: "Color tunable phosphorescent light-emitting diodes based on iridium complexes with substituted 2-phenylbenzothiozoles as the cyclometalated ligands", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》, vol. 689, 11 November 2004 (2004-11-11), pages 4882 - 4888, XP004670320, DOI: doi:10.1016/j.jorganchem.2004.07.003 * |
| 黄嘉 等: "2-(对叔丁基-苯基)-苯并噻唑合铱(Ⅲ )的乙酰丙酮配合物的合成及性质", 《分子科学学报》, vol. 23, no. 5, 31 October 2007 (2007-10-31), pages 328 - 331 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106158416A (en) * | 2016-08-22 | 2016-11-23 | 电子科技大学 | A kind of Graphene/zinc oxide composite material of core-shell structure is the preparation method of the ultracapacitor of negative pole |
| CN106158416B (en) * | 2016-08-22 | 2019-01-15 | 四川英能基科技有限公司 | A kind of graphene/zinc oxide composite material of core-shell structure is the preparation method of the supercapacitor of cathode |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI438195B (en) | A compound for an organic electroluminescent device, and an organic electroluminescent device using the same | |
| CN101274916B (en) | Multifunctional bipolar carrier transmission material and application thereof | |
| TWI662043B (en) | Organic metal compound and organic light-emitting device | |
| CN103965876A (en) | Green-yellow light-emitting organic electroluminescent material, its preparation method and organic electroluminescent device | |
| CN104119396A (en) | Blue organic electrophosphorescent material iridium metal complex, preparation method thereof and organic electroluminescent device | |
| CN103965878A (en) | Green-yellow light-emitting organic electroluminescent material, its preparation method and organic electroluminescent device | |
| CN103965884A (en) | Blue light-emitting organic electroluminescent material and its preparation method and use | |
| CN104877664A (en) | Blue organic electrophosphorescent material iridium complex and its preparation method and organic electroluminescent device | |
| CN103965251A (en) | Red organic electroluminescent material and its preparation method and application | |
| CN104293342A (en) | Blue-light organic electrophosphorescent material, preparation method and application thereof | |
| CN104177434A (en) | Red phosphorescence iridium complexes, preparing method thereof and organic electroluminescence device | |
| CN103965875A (en) | Red organic electroluminescent material and its preparation method and application | |
| CN103965872A (en) | Red organic electroluminescent material and its preparation method and application | |
| CN104177410A (en) | Blue electrophosphorescent material iridium metal complex, preparation method and organic electroluminescent device | |
| CN104876965A (en) | Blue organic electrophosphorescent material iridium complex and its preparation method and organic electroluminescent device | |
| CN104876964A (en) | Blue organic electrophosphorescent material iridium complex and its preparation method and organic electroluminescent device | |
| CN103965879A (en) | Blue light-emitting organic electroluminescent material, its preparation method and organic electroluminescent device | |
| CN104877663A (en) | Blue organic electrophosphorescent material iridium complex and its preparation method and organic electroluminescent device | |
| CN104876963A (en) | Blue organic electrophosphorescent material iridium metal complex, preparation method thereof, and organic electroluminescent device | |
| CN103965881A (en) | Blue light-emitting organic electroluminescent material, its preparation method and organic electroluminescent device | |
| CN104945442A (en) | Blue organic electrophosphorescent metal iridium complex, preparation method thereof and organic electroluminescent device | |
| CN104945439A (en) | Blue organic electrophosphorescent metal iridium complex, preparation method thereof and organic electroluminescent device | |
| CN103965874A (en) | Red organic electroluminescent material and its preparation method and application | |
| CN104177435A (en) | Red phosphorescence iridium complexes, preparing method thereof and organic electroluminescence device | |
| CN104178114A (en) | Red phosphorescence iridium complexes, preparing method thereof and organic electroluminescence device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140806 |