CN104178111A - Blue light organic electroluminescent material, and preparation method and application thereof - Google Patents
Blue light organic electroluminescent material, and preparation method and application thereof Download PDFInfo
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- CN104178111A CN104178111A CN201310193062.4A CN201310193062A CN104178111A CN 104178111 A CN104178111 A CN 104178111A CN 201310193062 A CN201310193062 A CN 201310193062A CN 104178111 A CN104178111 A CN 104178111A
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Abstract
The invention belongs to the field of photoelectric materials, and specifically relates to a blue light organic electroluminescent material. A structural formula (P) is shown in the description. In the formula, R represents alkoxy of C1-C20. The blue light organic electroluminescent material has a relatively high LUMO energy level and relatively low HOMO energy level, and is beneficial to blue shift of luminescent wavelengths of the material. The blue light organic electroluminescent material also has relatively high phosphorescence quantum efficiency, relatively good solubility and processability. The invention also provides a preparation method of the blue light organic electroluminescent material, and an application of the blue light organic electroluminescent material in an organic electroluminescent device.
Description
Technical field
The present invention relates to field of photovoltaic materials, be specifically related to a kind of blue-ray organic electroluminescent material and its preparation method and application.
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.Due to the restriction of the statistical theory that spinned, the theoretical internal quantum efficiency limit of fluorescent material is only 25%, how to make full use of all the other phosphorescence of 75% and realizes higher luminous efficiency and become the hot research direction in this field after this.The title complex of iridium, ruthenium, platinum etc. can obtain very high emitted energy from the triplet state of self, and metal iridium (III) compound wherein, due to good stability, in building-up process, reaction conditions is gentle, and there is very high electroluminescent properties, in research process subsequently, accounting for dominant position always.
Holmes R J, disclosed two [2-(the 4' of the people such as Forrest S R, 6'-difluorophenyl) pyridine-N, C2'] (2-pyridine formyl) close iridium (FIrpic, its structural formula is as follows) (App.Phys.Lett., 2003,82 (15): be 2422-2424) that report is maximum at present, be the best blue light organic phosphorescent electroluminescent materials of over-all properties, but the blue light that FIrpic sent out is sky blue, blue light color purity is not good enough yet, the CIE of the OLED device of making of FIrpic is (0.13～0.17,0.29～0.39) between, change this and the very large gap of CIE (0.137,0.084) existence of standard blue light.
2005, Taiwan's scholars Yeh S-J, Wu M-F, the people such as Chen C-T disclose the two [2-(4' of iridium metal complex, 6'-difluorophenyl) pyridine-N, C2'] (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-yl) pyrroles) close iridium (FIrN4, its structural formula is as follows) (Adv.Mater., 2005,17 (3): 285-289), FIrN4 is a kind of with 5-(2'-pyridyl)-1,2,3,4-tetrazolium is the blue light organic phosphorescent electroluminescent materials of assistant ligand, and the FIrN4 device of identity unit structure is compared with FIrpic device, and the blue light color purity of FIrN4 device is higher.This is due to FIrN4 high field intensity assistant ligand 5-(2'-pyridyl)-1,2,3, the introducing of 4-tetrazolium effectively blue shift the emission wavelength of material, thereby improved blue light color purity, this makes 5-(2'-pyridyl)-1,2,3,4-tetrazolium becomes one of different first-selected assistant ligand of joining type blue phosphorescent complex of iridium luminescent material.
2009, the people such as the Youngjin Kang of Korea S reported containing complex of iridium three (2', 6'-bis-is fluoro-2,3'-dipyridyl) and have closed iridium (Ir (dfpypy)
3, its structural formula is as follows) and blue phosphorescent material (Inorg.Chem.2009,48,1030-1037), compare Ir (dfpypy) with Firpic
3cyclic metal complexes agent structure is dipyridyl group, and the N atom on this group has been replaced the CH on Firpic phenyl ring, because the electronegativity of N is better than C, causes Ir (dfpypy)
3the HOMO energy level of material further declines, emission wavelength blue shift, its CH
2cl
2solution maximum emission wavelength at room temperature reaches 438nm, phosphorescence quantum yield Φ
pLreach 0.71, chromaticity coordinates value CIE is (0.14,0.12), x, the equal <0.15 of y value.The CH that this explanation adopts N to replace on phenyl ring in main part is the effective ways that obtain novel high color purity blue emitting phosphor material.
In order to make device obtain full-color demonstration, generally must obtain ruddiness, green glow and the blue light material of excellent performance simultaneously.Generally speaking, the development of blue phosphorescent material lags behind ruddiness and green glow.So the blue-ray organic electroluminescent material of developing high color purity is still a large focus of OLED research field.
Summary of the invention
For addressing the above problem, the invention provides a kind of blue-ray organic electroluminescent material, this material has good blue light luminous efficiency and good processing characteristics.The present invention also provides the preparation method of this blue-ray organic electroluminescent material and the application in organic electroluminescence device thereof.
First aspect, the invention provides a kind of blue-ray organic electroluminescent material, and structural formula is as shown in P:
In formula, R is C
1～C
20alkoxyl group, in described structural formula P, the structural formula of cyclic metal complexes is:
in formula, n=1～20.
This blue-ray organic electroluminescent material is that a class contains complex of iridium material, comprises cyclic metal complexes agent structure 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl) pyrimidine and assistant ligand 5-(2'-pyridyl)-pyrrotriazole, from luminous efficiency: described cyclic metal complexes agent structure, pyrimidyl is the N heterocycle of high lumo energy, two electrophilic trifluoromethyls on pyridyl and ring thereof can reduce the HOMO energy level of material, the effective blue shift that is conducive to material emission wavelength, secondly, on pyrimidine ring, the electronic property of giving of alkoxyl group can further improve the blue light emitting performance of material, on the other hand, the introducing of this alkoxyl group can produce certain space steric effect, thereby the self-quenching phenomenon of the direct effect between minimizing atoms metal and triplet exciton, improve the phosphorescence quantum yield of material, and then raising luminous efficiency, in addition, high field intensity assistant ligand 5-(2'-pyridyl)-1, 2, 3, 4-tetrazolium can make the more acceptant electronics of material, thereby further improve the luminous efficiency of material, angle from materials processing: pyrimidine ring, the oxyalkyl chain of different lengths can increase the solvability of material in organic solvent, the different type title complex of joining can reduce evaporation temperature, increase film-forming properties, thereby improved Drawing abillity and improved the stability of device.
Second aspect, the present invention also provides a kind of preparation method of blue-ray organic electroluminescent material, comprises the steps:
S10, the compd A and the compd B that provide following structural formula to represent:
In formula, R is C
1～C
20alkoxyl group, described structural formula A is
in formula, n=1～20;
Under S20, protection of inert gas; described compd A and compd B are dissolved in the first organic solvent that contains palladium catalyst and alkali by the mol ratio of 1:1～1:1.5; obtain reaction solution; described reaction solution carried out Suzuki linked reaction after 10～15 hours at 80～90 ℃; separation and purification reaction solution; obtain Compound C, its structural formula is as shown in C:
In formula, R is C
1～C
20alkoxyl group, described structural formula C is:
in formula, n=1～20;
Under S30, protection of inert gas; it is in the cellosolvo of 3:1 and the mixed solvent of water that described Compound C and three hydration iridous chlorides are dissolved in to volume ratio by the mol ratio of 2:1～3:1; be heated to subsequently at 100 ℃ back flow reaction after 24 hours; be cooled to room temperature; separation and purification; obtain Compound D, its structural formula is as shown in D:
In formula, R is C
1～C
20alkoxyl group, described structural formula D is:
In formula, n=1～20;
S40, the compd E that provides following structural formula to represent:
Under protection of inert gas; described Compound D and compd E are dissolved in the second organic solvent that contains sodium methylate or sodium ethylate by the mol ratio of 1:2～1:3; obtain mixing solutions; described mixing solutions carried out Suzuki linked reaction after 8～20 hours at 40～84 ℃; separation and purification; obtain blue-ray organic electroluminescent material, its structural formula is as shown in P:
In formula, R is C
1～C
20alkoxyl group, in described structural formula P, the structural formula of cyclic metal complexes is:
in formula, n=1～20.
Particularly, in described S20, the reaction formula of described reaction is:
In described S30, the reaction formula of described reaction is:
In described S40, the reaction formula of described reaction is:
In above-mentioned S20, S30 and S40, n=1～20.
Preferably, in described S20, the concentration of described compd A in reaction solution is 0.07～0.2mol/L; Described the first organic solvent is DMF (DMF) or toluene.
Preferably, in described S20, the volume ratio of described the first organic solvent and wet chemical is about 2:1.
Preferably, in described S20, the volume ratio of described the first organic solvent and aqueous sodium carbonate is about 2:1.
Preferably, in described S20, described palladium catalyst is that dichloro two (triphenylphosphine) is changed palladium or four (triphenylphosphine) and closed palladium, the mole dosage of described palladium catalyst is compd A 3%～5% times; Described alkali is wet chemical or aqueous sodium carbonate, the mole dosage of described alkali is compd A 1～3 times.
Preferably, in described S20, described purification procedures comprises: reaction solution is cooled to after room temperature, adopt dichloromethane extraction, then be washed with water to neutrality, again after anhydrous magnesium sulfate drying, filtration obtains filtrate, gained filtrate obtains crude product after removing desolventizing under reduced pressure, it is separated that the sherwood oil that the sherwood oil that crude product is 1:5～1:6 by volume ratio is 1:6 with the mixed solution of methylene dichloride or volume ratio and the mixed solution of ethyl acetate are that eluent carries out silica gel column chromatography, obtains described Compound C.
Preferably, in described S30, the concentration of described Compound C in reaction solution is 0.05～0.1mol/L.
Preferably, in described S30, described purification procedures comprises: question response stops being chilled to after room temperature, rotates and steams except partial solvent, adds appropriate distilled water, filters and obtains solid, and solid is used distilled water, methanol wash successively, after being dried, obtains described Compound D.
Preferably, in described S40, described the second organic solvent is 1,2-ethylene dichloride, methylene dichloride or trichloromethane.
Preferably, in described S40, the concentration of described Compound D in mixing solutions is 0.01～0.02mol/L, the mole dosage of described sodium methylate or sodium ethylate is Compound D 8～12 times.
Preferably, in described S40, described purification procedures comprises: question response stops being chilled to after room temperature, and concentrated remove portion solvent, adds appropriate distilled water, has solid to separate out; Filter to collect crude product, after crude product uses deionized water, methanol wash for several times successively, then through the mixed solvent recrystallization of methylene dichloride and dehydrated alcohol, obtain described blue-ray organic electroluminescent material.
The preparation method of a kind of blue-ray organic electroluminescent material provided by the invention is simple, handled easily.
In subsequent embodiment, for convenience of statement, compd A, C, D, P use respectively compd A 1, A2, A3, A4 C1, C2, C3, C4 ... D1, D2, D3, D4 P1, P2, P3, P4 ... represent, concrete name is as the criterion with each embodiment.
The third aspect, the present invention also provides a kind of organic electroluminescence device, comprises luminescent layer, and in described luminescent layer, doped with the blue-ray organic electroluminescent material as described in first aspect, structural formula is as shown in P:
In formula, R is C
1～C
20alkoxyl group, in described structural formula P, the structural formula of cyclic metal complexes is:
in formula, n=1～20.
Organic electroluminescence device provided by the invention contains the blue-ray organic electroluminescent material of structural formula as shown in P, and this material has higher lumo energy and lower HOMO energy level, can make device have good blue light emitting performance; In addition, this material filming performance is good, easily processing.
A kind of blue-ray organic electroluminescent material provided by the invention and its preparation method and application, its beneficial effect having is:
(1) blue-ray organic electroluminescent material provided by the invention comprises cyclic metal complexes agent structure 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl) pyrimidine and assistant ligand 5-(2'-pyridyl)-pyrrotriazole, in described cyclic metal complexes agent structure, pyrimidyl is the N heterocycle of high lumo energy, two electrophilic trifluoromethyls on pyridyl and ring thereof are conducive to reduce the HOMO energy level of material, thereby the effective blue shift of the emission wavelength that makes material, secondly, on pyrimidine ring, the electronic property of giving of alkoxyl group can further improve the blue light emitting performance of material, on the other hand, the introducing of this alkoxyl group can produce certain space steric effect, thereby the self-quenching phenomenon of the direct effect between minimizing atoms metal and triplet exciton, improve the phosphorescence quantum yield of material, and then raising luminous efficiency, in addition, high field intensity assistant ligand 5-(2'-pyridyl)-1, 2, 3, 4-tetrazolium can make the more acceptant electronics of material, thereby further improve the luminous efficiency of material,
(2) blue-ray organic electroluminescent material provided by the invention, introducing due to different lengths oxyalkyl chain on pyrimidine ring, improved the solubility property of material in organic solvent, the different type title complex of joining can reduce evaporation temperature, can increase the film forming properties of material, thereby improve Drawing abillity and improve the stability of device;
(3) blue-ray organic electroluminescent material synthetic reaction condition provided by the invention is gentle, and technique is simple, is easy to preparation;
(4) organic electroluminescence device provided by the invention has good blue light luminous efficiency and higher stability.
Accompanying drawing explanation
Fig. 1 is the preparation flow schematic diagram of the blue-ray organic electroluminescent material that provides of the embodiment of the present invention 1;
Fig. 2 is the utilizing emitted light spectrogram of the blue-ray organic electroluminescent material that provides of the embodiment of the present invention 1;
Fig. 3 is the structural representation of the organic electroluminescence device that provides of the embodiment of the present invention 4.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
The present embodiment provides a kind of two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-methoxy pyrimidine-N, C
4') (5-(2'-pyridyl)-pyrrotriazole) close complex of iridium, its chemical structure is as shown in P1:
The preparation process of above-mentioned P1 is as follows:
Synthesizing S10, Compound C 1(2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-methoxy pyrimidine)
The bromo-5-methoxy pyrimidine of compd A 1(2-that provides following structural formula to represent) and compd B (2,6-bis-(trifluoromethyl) pyridine-3-boric acid):
Under nitrogen protection, by compd A 1 (1.89g, 10mmol), compd B (3.11g, 12mmol) and Pd (PPh
3)
4(0.58mg, 0.5mmol) is dissolved in the toluene of 35mL, then adds 15mL to contain the aqueous solution of salt of wormwood (2.76g, 20mmol), and at 90 ℃, stirring reaction is 10 hours; Question response liquid cooling is to room temperature, with dichloromethane extraction, separatory, then be washed to neutrality, again with filtering after anhydrous magnesium sulfate drying, filtrate obtains crude product through removing desolventizing under reduced pressure, and it is separated that the sherwood oil that crude product is 1:5 by volume ratio again and the mixed solution of methylene dichloride are that eluent carries out silica gel column chromatography, obtains 1.29g Compound C 1 after dry, yield is 39.9%, and reaction formula is as follows:
The Structural Identification result of Compound C 1 is as follows:
Mass spectrum (MS m/z): 323.1 (M+)
Ultimate analysis: C
12h
7f
6n
3o
Theoretical value: C, 44.60; H, 2.18; F, 35.27; N, 13.00; O, 4.95
Measured value: C, 44.66; H, 2.11; F, 35.29; N, 13.03; O, 4.91
The resulting product C 1 of the above-mentioned reaction of above data acknowledgement is 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-methoxy pyrimidine;
S20, Compound D 1(part be 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-methoxy pyrimidine containing iridium dichloro dimer) synthetic
Under nitrogen protection, it is in the cellosolvo of 3:1 and the mixed solvent of water that Compound C 1 (1.29g, 4mmol) and three hydration iridous chlorides (0.70g, 2mmol) are dissolved in to 40mL volume ratio, and stirring reaction 24 hours refluxes at 100 ℃; Be chilled to after room temperature, rotate and steam except partial solvent, then add appropriate distilled water, filter and obtain solid, solid is used distilled water, methanol wash successively, obtains the Compound D 1 of 0.71g after being dried, and yield is 40.7%, and reaction formula is as follows:
S30, P1(two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-methoxy pyrimidine-N, C
4') (5-(2'-pyridyl)-pyrrotriazole) close complex of iridium) and synthetic
The compd E (5-(2'-pyridyl)-pyrrotriazole) that provides following structural formula to represent:
Under nitrogen protection, by Compound D 1 (0.87g, 0.5mmol) and compd E (0.18g, 1.25mmol) be dissolved in 1 of 15mL, in 2-ethylene dichloride, drip subsequently 10mL containing 1 of sodium methylate (0.27g, 5mmol), 2-dichloroethane solution, is heated with stirring to 84 ℃ of reflux state reactions 8 hours; Naturally be chilled to after room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, there is solid to separate out, filter, collect crude product, crude product is used deionized water, methanol wash for several times successively, the P1 that obtains 0.37g purifying through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 37.6%, reaction formula is as follows:
The Structural Identification result of compound P1 is as follows:
Mass spectrum (MS m/z): 983.1 (M+)
Ultimate analysis: C
30h
16f
12irN
11o
2
Theoretical value: C, 36.67; H, 1.64; F, 23.20; Ir, 19.56; N, 15.68; O, 3.26
Measured value: C, 36.71; H, 1.61; F, 23.15; Ir, 19.59; N, 15.64; O, 3.30
The resulting product P 1 of the above-mentioned reaction of above data acknowledgement is two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-methoxy pyrimidine-N, C4') (5-(2'-pyridyl)-pyrrotriazole) and closes complex of iridium.
As shown in Figure 2, transverse axis is wavelength (Wavelength, the nm of unit), and the longitudinal axis is standardized photoluminescence intensity (Normalized PL intensity), and at 298K temperature, P1 (～10
-6m) at CH
2cl
2in solution, the maximum emission peak of emmission spectrum, at 433nm place, has an acromion at 465nm place simultaneously, and this P1 that shows that the present embodiment provides can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.
In addition, product P 1 (～10
-6m) CH
2cl
2solution is at 298K temperature, with the CH of the FIrpic under the same terms
2cl
2solution is standard (Φ
pL=0.26), record the Φ of P1
pL=0.11, the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency.
Embodiment 2
The present embodiment provides a kind of two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-4-hexyloxy pyrimidine-N, C4') (5-(2'-pyridyl)-pyrrotriazole) to close complex of iridium, and its chemical structure is as shown in P2:
The preparation process of above-mentioned P2 is as follows:
Synthesizing S10, Compound C 2(2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-hexyloxy pyrimidine)
The bromo-5-of compd A 2(2-that following structural formula represents oxygen yl pyrimidines is provided) and compd B (2,6-bis-(trifluoromethyl) pyridine-3-boric acid):
Under nitrogen protection, by compd A 2 (1.30g, 5mmol), compd B (1.29g, 5mmol) and Pd (PPh
3)
2cl
2(0.14mg, 0.2mmol) is dissolved in the DMF of 35mL, then adds 15mL to contain the aqueous solution of salt of wormwood (2.07g, 15mmol), stirs 12 hours at 80 ℃; Question response liquid cooling is to room temperature, with dichloromethane extraction, separatory, then be washed to neutrality, again with filtering after anhydrous magnesium sulfate drying, filtrate obtains crude product through removing desolventizing under reduced pressure, and it is separated that the sherwood oil that crude product is 1:5 by volume ratio again and the mixed solution of methylene dichloride are that eluent carries out silica gel column chromatography, obtains 0.39g Compound C 1 after dry, yield is 19.8%, and reaction formula is as follows:
The Structural Identification result of Compound C 2 is as follows:
Mass spectrum (MS m/z): 393.1 (M+)
Ultimate analysis: C
17h
17f
6n
3o
Theoretical value: C, 51.91; H, 4.36; F, 28.98; N, 10.68; O, 4.07
Measured value: C, 51.96; H, 4.30; F, 29.03; N, 10.62; O, 4.09
The resulting product C 2 of the above-mentioned reaction of above data acknowledgement is 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-4-hexyloxy pyrimidines.
S20, Compound D 2(part be 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-4-hexyloxy pyrimidine containing iridium dichloro dimer) synthetic
It is in the cellosolvo of 3:1 and the mixed solvent of water that Compound C 2 (0.64g, 2.2mmol) and three hydration iridous chlorides (0.36g, 1mmol) are dissolved in to 25mL volume ratio, and stirring reaction 24 hours refluxes at 100 ℃; Be chilled to after room temperature, rotate and steam except partial solvent, then add appropriate distilled water, filter and obtain solid, solid is used distilled water, methanol wash successively, obtains the Compound D 2 of 0.16g after being dried, and yield is 15.8%, and reaction formula is as follows:
S30, P2(two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-4-hexyloxy pyrimidine-N, C
4') (5-(2'-pyridyl)-pyrrotriazole) close complex of iridium) and synthetic
Compd E is as described in Example 1 provided;
Under nitrogen protection, by Compound D 1 (0.81g, 0.4mmol) and compd E (0.12g, 0.8mmol) be dissolved in the methylene dichloride of 15mL, drip subsequently 10mL containing the dichloromethane solution of sodium ethylate (0.22g, 3.2mmol), stirring heating, at 40 ℃, back flow reaction is 20 hours; Naturally be chilled to after room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, there is solid to separate out, filter, collect crude product, crude product is used deionized water, methanol wash for several times successively, the P2 that obtains 0.27g purifying through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 30.0%, reaction formula is as follows:
The Structural Identification result of compound P2 is as follows:
Mass spectrum (MS m/z): 1123.2 (M+)
Ultimate analysis: C
40h
36f
12irN
11o
2
Theoretical value: C, 42.78; H, 3.23; F, 20.30; Ir, 17.12; N, 13.72; O, 2.85
Measured value: C, 42.74; H, 3.28; F, 20.23; Ir, 17.17; N, 13.75; O, 2.83
The resulting product P 2 of the above-mentioned reaction of above data acknowledgement is two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-4-hexyloxy pyrimidine-N, C
4') (5-(2'-pyridyl)-pyrrotriazole) close complex of iridium.
At 298K temperature, P2 (～10
-6m) CH
2cl
2in solution, the maximum emission peak of emmission spectrum, at 442nm place, has an acromion at 472nm place simultaneously; In addition, 10
-6the CH of M product P 2
2cl
2solution is at 298K temperature, with the CH of the FIrpic under the same terms
2cl
2solution is standard (Φ
pL=0.26), record the Φ of P2
pL=0.09.
Embodiment 3
The present embodiment provides a kind of two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-eicosane oxygen yl pyrimidines-N, C
4') (5-(2'-pyridyl)-pyrrotriazole) close complex of iridium, its chemical structure is as shown in P3:
The preparation process of above-mentioned P3 is as follows:
Synthesizing S10, Compound C 3(2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-eicosane oxygen yl pyrimidines)
The compound A-13 (the bromo-5-eicosane of 2-oxygen yl pyrimidines) and the compd B (2,6-bis-(trifluoromethyl) pyridine-3-boric acid) that provide following structural formula to represent:
Under nitrogen protection, by compound A-13 (0.91g, 2mmol), compd B (0.78g, 3mmol) and Pd (PPh
3)
4(0.12mg, 0.1mmol) is dissolved in the toluene of 20mL, then adds 10mL to contain the aqueous solution of sodium carbonate (0.21g, 2mmol), stirs 15 hours at 90 ℃; Question response liquid cooling is to room temperature, with dichloromethane extraction, separatory, then be washed to neutrality, again with filtering after anhydrous magnesium sulfate drying, filtrate obtains crude product through removing desolventizing under reduced pressure, and it is separated that the sherwood oil that crude product is 1:6 by volume ratio again and the mixed solution of ethyl acetate are that eluent carries out silica gel column chromatography, obtains 0.12g Compound C 1 after dry, yield 10.2%, reaction formula is as follows:
The Structural Identification result of Compound C 3 is as follows:
Mass spectrum (MS m/z): 589.3 (M+)
Ultimate analysis: C
31h
45f
6n
3o
Theoretical value: C, 63.14; H, 7.69; F, 19.33; N, 7.13; O, 2.71
Measured value: C, 63.18; H, 7.62; F, 19.38; N, 7.10; O, 2.72
The resulting C3 of the above-mentioned reaction of above data acknowledgement is 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-eicosane oxygen yl pyrimidines;
S20's, compound d3 (part be 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-eicosane oxygen yl pyrimidines containing iridium dichloro dimer) is synthetic
It is in the cellosolvo of 3:1 and the mixed solvent of water that Compound C 3 (0.88g, 1.5mmol) and three hydration iridous chlorides (0.18g, 0.5mmol) are dissolved in to 30mL volume ratio, and stirring reaction 24 hours refluxes at 100 ℃; Be chilled to after room temperature, rotate and steam except partial solvent, then add appropriate distilled water, filter and obtain solid, solid is used distilled water, methanol wash successively, obtains the compound d3 of 0.07g after being dried, and yield is 10.0%, and reaction formula is as follows:
S30, P3(two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-eicosane oxygen yl pyrimidines-N, C
4') (5-(2'-pyridyl)-pyrrotriazole) close complex of iridium) and synthetic
Compd E is as described in Example 1 provided;
Under nitrogen protection, by compound d3 (0.84g, 0.3mmol) and compd E (0.13g, 0.9mmol) be dissolved in the trichloromethane of 20mL, drip subsequently 10mL containing the chloroform soln of sodium methylate (0.19g, 3.6mmol), be heated with stirring to 62 ℃ of back flow reaction 15 hours; Naturally be chilled to after room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, there is solid to separate out, filter, collect crude product, crude product is used deionized water, methanol wash for several times successively, the P3 that obtains 0.08g purifying through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 8.8%, reaction formula is as follows:
The Structural Identification result of compound P3 is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1515.7 (M+)
Ultimate analysis: C
68h
92f
12irN
11o
2
Theoretical value: C, 53.88; H, 6.12; F, 15.04; Ir, 12.68; N, 10.16; O, 2.11
Measured value: C, 53.84; H, 6.17; F, 15.02; Ir, 12.72; N, 10.11; O, 2.14
The resulting product P 3 of the above-mentioned reaction of above data acknowledgement is two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-eicosane oxygen yl pyrimidines-N, C
4') (5-(2'-pyridyl)-pyrrotriazole) close complex of iridium.
At 298K temperature, P3 (～10
-6m) CH
2cl
2in solution, the maximum emission peak of emmission spectrum, at 454nm place, has an acromion at 484nm place simultaneously; In addition, 10
-6the CH of M product P 3
2cl
2solution is at 298K temperature, with the CH of the FIrpic under the same terms
2cl
2solution is standard (Φ
pL=0.26), record the Φ of P2
pL=0.06.
Embodiment 4
The present embodiment be take the doping object that title complex P1 that the embodiment of the present invention 1 provides is luminescent layer, prepare a kind of organic electroluminescence device, as shown in Figure 3, the structure of this organic electroluminescence device comprises transparent anode 301, hole injection layer 302, hole transmission layer 303, electronic barrier layer 304, luminescent layer 305, hole blocking layer 306, electron transfer layer 307, electronic injection buffer layer 308, the negative electrode 309 stacking gradually.
The preparation technology of this organic electroluminescence device comprises:
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, by vacuum evaporation, preparing successively a layer thickness on anode 301 is 4 of 40nm, 4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA) is as hole injection layer 302, a layer thickness is the N of 20nm, two (1-the naphthyl)-N of N'-, N'-phenylbenzene benzidine (NPB) is as hole transmission layer 303, a layer thickness is 1 of 10nm, two (9-carbazyl) benzene (mCP) of 3-is as electronic barrier layer 304, with a layer thickness mCP mixing material doped with 7wt%P1 that is 30nm as luminescent layer 305, on this luminescent layer 305, vacuum evaporation a layer thickness is successively 10nm again 2, 9-dimethyl-4, 7-phenylbenzene-phenanthrolene (BCP) is as hole blocking layer 306, thickness is three (oxine) aluminium (Alq of 35nm
3) lithium fluoride (LiF) that is 1nm as electron transfer layer 307, thickness is as electronic injection buffer layer 308, finally on buffer layer, adopts the metallic aluminium (Al) that vacuum plating techniques of deposition thickness is 120nm, as the negative electrode 309 of device.Therefore, the concrete structure of this organic electroluminescence device also can be expressed as ITO (100nm)/m-MTDATA (40nm)/NPB (20nm)/mCP (10nm)/mCP:7wt%P1 (30nm)/BCP (10nm)/Alq
3(35nm)/LiF (1nm)/Al (120nm); Wherein, P1 is the title complex that the embodiment of the present invention 1 makes, and slash "/" represents laminate structure.
By Keithley source measuring system (Keithley2400Sourcemeter), tested the electric current-brightness-voltage characteristic of above-mentioned organic electroluminescence device, with French its electroluminescent spectrum of the JY SPEX CCD3000 of company spectrometer measurement, all measurements all complete in atmosphere at room temperature, the maximum external quantum efficiency that records organic electroluminescence device is 9.8%, and maximum lumen efficiency is 7.3lm/W.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. a blue-ray organic electroluminescent material, is characterized in that, structural formula is as shown in P:
In formula, R is C
1～C
20alkoxyl group.
2. a preparation method for blue-ray organic electroluminescent material, is characterized in that, comprises the steps:
S10, the compd A and the compd B that provide following structural formula to represent:
In formula, R is C
1～C
20alkoxyl group;
Under S20, protection of inert gas; described compd A and compd B are dissolved in the first organic solvent that contains palladium catalyst and alkali by the mol ratio of 1:1～1:1.5; obtain reaction solution; described reaction solution carried out Suzuki linked reaction after 10～15 hours at 80～90 ℃; separation and purification reaction solution; obtain Compound C, its structural formula is as shown in C:
In formula, R is C
1～C
20alkoxyl group;
Under S30, protection of inert gas; it is in the cellosolvo of 3:1 and the mixed solvent of water that described Compound C and three hydration iridous chlorides are dissolved in to volume ratio by the mol ratio of 2:1～3:1; be heated to subsequently at 100 ℃ back flow reaction after 24 hours; be cooled to room temperature; separation and purification; obtain Compound D, its structural formula is as shown in D:
In formula, R is C
1～C
20alkoxyl group;
S40, the compd E that provides following structural formula to represent:
Under protection of inert gas; described Compound D and compd E are dissolved in the second organic solvent that contains sodium methylate or sodium ethylate by the mol ratio of 1:2～1:3; obtain mixing solutions; described mixing solutions carried out Suzuki linked reaction after 8～20 hours at 40～84 ℃; separation and purification; obtain blue-ray organic electroluminescent material, its structural formula is as shown in P:
In formula, R is C
1～C
20alkoxyl group.
3. the preparation method of blue-ray organic electroluminescent material as claimed in claim 2, is characterized in that, in described S20, the concentration of described compd A in reaction solution is 0.07～0.2mol/L; Described the first organic solvent is DMF or toluene.
4. the preparation method of blue-ray organic electroluminescent material as claimed in claim 2, it is characterized in that, in described S20, described palladium catalyst is that dichloro two (triphenylphosphine) is changed palladium or four (triphenylphosphine) and closed palladium, the mole dosage of described palladium catalyst is compd A 3%～5% times; Described alkali is wet chemical or aqueous sodium carbonate, the mole dosage of described alkali is compd A 1～3 times.
5. the preparation method of blue-ray organic electroluminescent material as claimed in claim 2, it is characterized in that, in described S20, described purification procedures comprises: reaction solution is cooled to after room temperature, adopt dichloromethane extraction, then be washed with water to neutrality, again after anhydrous magnesium sulfate drying, filtration obtains filtrate, gained filtrate obtains crude product after removing desolventizing under reduced pressure, it is separated that the sherwood oil that the sherwood oil that crude product is 1:5～1:6 by volume ratio is 1:6 with the mixed solution of methylene dichloride or volume ratio and the mixed solution of ethyl acetate are that eluent carries out silica gel column chromatography, obtain described Compound C.
6. the preparation method of blue-ray organic electroluminescent material as claimed in claim 2, it is characterized in that, in described S30, described purification procedures comprises: question response stops being chilled to after room temperature, rotation is steamed except partial solvent, adds appropriate distilled water, filters and obtains solid, solid is used distilled water, methanol wash successively, after being dried, obtains described Compound D.
7. the preparation method of blue-ray organic electroluminescent material as claimed in claim 2, is characterized in that, in described S40, described the second organic solvent is 1,2-ethylene dichloride, methylene dichloride or trichloromethane.
8. the preparation method of blue-ray organic electroluminescent material as claimed in claim 2, it is characterized in that, in described S40, the concentration of described Compound D in mixing solutions is 0.01～0.02mol/L, the mole dosage of described sodium methylate or sodium ethylate is Compound D 8～12 times.
9. the preparation method of blue-ray organic electroluminescent material as claimed in claim 2, is characterized in that, in described S40, described purification procedures comprises: question response stops being chilled to after room temperature, and concentrated remove portion solvent, adds appropriate distilled water, has solid to separate out; Filter to collect crude product, crude product is used after deionized water, methanol wash successively, then through the mixed solvent recrystallization of methylene dichloride and dehydrated alcohol, obtains described blue-ray organic electroluminescent material.
10. an organic electroluminescence device, comprises luminescent layer, it is characterized in that, in described luminescent layer, doped with blue-ray organic electroluminescent material as claimed in claim 1, structural formula is as shown in P:
In formula, R is C
1～C
20alkoxyl group.
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| JP2017088581A (en) * | 2015-11-17 | 2017-05-25 | 国立研究開発法人産業技術総合研究所 | Iridium complex and light emitting material and organic light emitting element prepared with the compound |
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