CN104178118A - Blue ray organic electroluminescent material and preparation method and application thereof - Google Patents
Blue ray organic electroluminescent material and preparation method and application thereof Download PDFInfo
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- CN104178118A CN104178118A CN201310196482.8A CN201310196482A CN104178118A CN 104178118 A CN104178118 A CN 104178118A CN 201310196482 A CN201310196482 A CN 201310196482A CN 104178118 A CN104178118 A CN 104178118A
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- 0 C=CN=C([C@]1NC(C(F)(F)F)=CC1C(F)(F)F)C=* Chemical compound C=CN=C([C@]1NC(C(F)(F)F)=CC1C(F)(F)F)C=* 0.000 description 3
- MHCICWYNEZRFMG-UHFFFAOYSA-N Bc1c(C(F)(F)F)nc(C(F)(F)F)cc1 Chemical compound Bc1c(C(F)(F)F)nc(C(F)(F)F)cc1 MHCICWYNEZRFMG-UHFFFAOYSA-N 0.000 description 1
- UZSGMOAEKSUOAL-UHFFFAOYSA-N Bc1nc(C)ccc1 Chemical compound Bc1nc(C)ccc1 UZSGMOAEKSUOAL-UHFFFAOYSA-N 0.000 description 1
- PPNOOHLLYBNCBO-UHFFFAOYSA-N C=CBc1c(C(F)(F)F)nc(C(F)(F)F)cc1 Chemical compound C=CBc1c(C(F)(F)F)nc(C(F)(F)F)cc1 PPNOOHLLYBNCBO-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention belongs to the field of photoelectric materials, and in particular relates to a blue ray organic electroluminescent material with the structural formula shown as P, wherein R is hydrogen atom or C1-C20 alkyl. The blue ray organic electroluminescent material has higher LUMO (lowest unoccupied molecular orbital) energy level and lower HOMO (highest occupied molecular orbital) energy level, is conducive to blue shift of material luminescent wavelength, and also has higher phosphorescence quantum efficiency and better dissolution properties and processing properties. The invention also provides a preparation method of the blue ray organic electroluminescent material and application of the blue ray organic electroluminescent material in organic electroluminescent devices.
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, reaction conditions gentleness in building-up process, 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): 2422-2424) be that report is maximum at present, also 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, the CIE of each OLED device of making is (0.13～0.17, 0.29～0.39) between, change, the CIE (0.137 of this and standard blue light, 0.084) there is very large gap.
2007, Taiwan's scholars Ching-Fong Shu, the people such as Yun Chi 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 (FIrfpy, its structural formula is as follows) (J.Mater.Chem., 2007, 17, 1692-1698), FIrfpy is a kind of with 2, the blue light organic phosphorescent electroluminescent materials that 4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles is assistant ligand, in dichloromethane solution, the maximum emission wavelength of FIrfpy is blue shifted to 461nm by the 470nm of FIrpic, blue light color purity is improved.This is due to FIrfpy high field intensity assistant ligand 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles's introducing effectively blue shift the emission wavelength of material, thereby improve blue light color purity, this makes 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles become 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.).Compared with Firpic, Ir (dfpypy)
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 always lags behind ruddiness and green glow.So the pure smooth electroluminescent organic 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 preparation method that the present invention also provides this blue-ray organic electroluminescent material with and application in organic electroluminescence device.
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 hydrogen atom or C
1～C
20alkyl, 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 is containing complex of iridium material, comprise cyclic metal complexes agent structure 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl) pyrimidine and assistant ligand 2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-yl) pyrroles, from luminous efficiency: described cyclic metal complexes agent structure, pyrimidyl is the N heterocycle of high lumo energy, the HOMO energy level that two electrophilic trifluoromethyls on pyridyl and ring thereof can reduce material is conducive to effective blue shift of material emission wavelength, secondly, on pyrimidine ring, the electronic property of giving of alkyl can further improve the blue light emitting performance of material, on the other hand, the introducing of this alkyl 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 2, 4-bis-(trifluoromethyl)-5-(pyridine-2 '-yl) pyrroles can make the more acceptant electronics of material, thereby further improve the luminous efficiency of material, angle from materials processing: pyrimidine ring, the alkyl chain of different lengths can increase the solvability of material in organic solvent, the different type title complex of joining can reduce evaporation temperature, increases film-forming properties, thereby has 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 hydrogen atom or C
1～C
20alkyl, 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 by the mol ratio of 1:1～1:2 in the first organic solvent that contains palladium catalyst and alkali; obtain reaction solution; described reaction solution carried out Suzuki linked reaction after 8～15 hours at 85～100 DEG C; separation and purification reaction solution; obtain Compound C, its structural formula is as shown in C:
In formula, R is C
1～C
20alkyl, 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 DEG C 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 hydrogen atom or C
1～C
20alkyl, 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 by the mol ratio of 1:2～1:3 in the second organic solvent that contains sodium methylate or sodium ethylate; obtain mixing solutions; described mixing solutions carried out Suzuki linked reaction after 6～20 hours at 40～135 DEG C; separation and purification; obtain blue-ray organic electroluminescent material, its structural formula is as shown in P:
In formula, R is hydrogen atom or C
1～C
20alkyl, 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 0.1～0.2mol/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%～6% times; Described alkali is wet chemical or aqueous sodium carbonate, the mole dosage of described alkali is compd A 2～4 times.
Preferably, in described S20, described purification procedures comprises: reaction solution is cooled to after room temperature, adopt dichloromethane extraction, be then washed with water to neutrality, then after anhydrous magnesium sulfate drying, filtration obtains filtrate, gained filtrate obtains crude product after removing desolventizing under reduced pressure, and the sherwood oil that crude product is 1:5～1:8 by volume ratio again and methylene dichloride mixed solution are that eluent carries out silica gel column chromatography and separates, and obtain described Compound C.
Preferably, in described S30, the concentration range of described Compound C in reaction system is 0.1～0.125mmol/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 and 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, specifically name and are 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, its structural formula is as shown in P:
In formula, R is hydrogen atom or C
1～C
20alkyl, 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 2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-yl) pyrroles, 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 alkyl can further improve the blue light emitting performance of material, on the other hand, the introducing of this alkyl 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 2, 4-bis-(trifluoromethyl)-5-(pyridine-2 '-yl) pyrroles 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, due to the introducing of different lengths alkyl chain on pyrimidine ring, improve 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 gentleness provided by the invention, technique is simple, is easy to preparation;
(4) organic electroluminescence device provided by the invention has good blue light luminous efficiency and higher stability.
Brief description of the drawings
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 5.
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, instead of whole embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art, 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) pyrimidine-N, C
4') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles) close complex of iridium, its chemical structure is as shown in P1:
The preparation process of above-mentioned P1 is as follows:
S10, Compound C 1(2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl) pyrimidine) synthetic
The compd A 1(2-bromo pyrimi piperidine 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 (0.80g, 5mmol), compd B (1.55g, 6mmol) and Pd (PPh
3)
4(0.35mg, 0.3mmol) is dissolved in the toluene of 15mL, then adds 10mL to contain the aqueous solution of salt of wormwood (1.66g, 12mmol), stirring reaction 8 hours at 100 DEG C; 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 the sherwood oil that crude product is 1:6 by volume ratio again and the mixed solution of methylene dichloride are that eluent carries out silica gel column chromatography and separates, and obtains 0.66g Compound C 1 after dry, yield 45%, reaction formula is as follows:
The Structural Identification result of Compound C 1 is as follows:
Mass spectrum (MS m/z): 293.0 (M+)
Ultimate analysis: C
11h
5f
6n
3
Theoretical value: C, 45.07; H, 1.72; F, 38.88; N, 14.33
Measured value: C, 45.12; H, 1.66; F, 38.93; N, 14.29
The product C 1 that the above-mentioned reaction of above data acknowledgement obtains is 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl) pyrimidine;
S20, Compound D 1(part be 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl) pyrimidine containing iridium dichloro dimer) synthetic
Under nitrogen protection, by Compound C 1 (0.73g, it is in the cellosolvo of 3:1 and the mixed solvent of water that 2.5mmol) He three hydration iridous chlorides (0.36g, 1mmol) are dissolved in 25mL volume ratio, and stirring reaction 24 hours refluxes at 100 DEG C; 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 0.45g after being dried, and yield is 55.4%, and reaction formula is as follows:
S30, P1(two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl) pyrimidine-N, C
4 ') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles) close complex of iridium) and synthetic
The compd E (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles) that provides following structural formula to represent:
Under nitrogen protection, by Compound D 1 (0.81g, 0.5mmol) and compd E (0.34g, 1.2mmol) be dissolved in the trichloromethane of 25mL, drip subsequently 10mL containing sodium ethylate (0.34g, chloroform soln 5mmol), is heated with stirring to 135 DEG C of back flow reaction 6 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 successively with deionized water, ether washing, the P1 that obtains 0.39g purifying through methylene dichloride and anhydrous methanol mixed solvent recrystallization, yield is 36.9%, reaction formula is as follows:
The Structural Identification result of compound P1 is as follows:
Mass spectrum (MS m/z): 1056.1 (M+)
Ultimate analysis: C
33h
13f
18irN
8
Theoretical value: C, 37.54; H, 1.24; F, 32.39; Ir, 18.21; N, 10.61
Measured value: C, 37.57; H, 1.21; F, 32.44; Ir, 18.18; N, 10.60
The product P 1 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl) pyrimidine-N, C
4') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles) close 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), at 298K temperature, and P1 (～10
-6m) at CH
2cl
2in solution, the maximum emission peak of emmission spectrum is at 436nm place, has an acromion at 468nm place simultaneously, and P1 that this demonstration the present embodiment provides can be used as blue light electroluminescent material and be widely used in the preparation field of 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=0.27, 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)-5-methylpyrimidine-N, C
4') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles) close complex of iridium, its chemical structure is as shown in P2:
The preparation process of above-mentioned P2 is as follows:
S10, Compound C 2(2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-methylpyrimidine) synthetic
The bromo-5-methylpyrimidine of compd A 2(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 2 (0.86g, 5mmol), compd B (1.29g, 5mmol) and Pd (PPh
3)
2cl
2(0.18mg, 0.25mmol) is dissolved in the DMF of 30mL, then adds 20mL to contain the aqueous solution of sodium carbonate (1.59g, 15mmol), stirs 10 hours at 90 DEG C; 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 the sherwood oil that crude product is 1:8 by volume ratio again and the mixed solution of methylene dichloride are that eluent carries out silica gel column chromatography and separates, and obtains 0.63g Compound C 1 after dry, yield is 41.0%, and reaction formula is as follows:
The Structural Identification result of Compound C 2 is as follows:
Mass spectrum (MS m/z): 307.1 (M+)
Ultimate analysis: C
12h
7f
6n
3
Theoretical value: C, 46.92; H, 2.30; F, 37.11; N, 13.68
Measured value: C, 46.95; H, 2.32; F, 37.04; N, 13.69
The product C 2 that the above-mentioned reaction of above data acknowledgement obtains is 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-methylpyrimidines;
S20, Compound D 2(part be 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-methylpyrimidine containing iridium dichloro dimer) synthetic
It is in the cellosolvo of 3:1 and the mixed solvent of water that Compound C 2 (0.92g, 3mmol) and three hydration iridous chlorides (0.36g, 1mmol) are dissolved in to 25mL volume ratio, and stirring reaction 24 hours refluxes at 100 DEG C; 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 0.42g after being dried, and yield is 50%, and reaction formula is as follows:
S30, P2(two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-methylpyrimidine-N, C
4') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles) close complex of iridium) and synthetic
Compd E is as described in Example 1 provided;
Under nitrogen protection, by Compound D 1 (0.84g, 0.5mmol) and compd E (0.28g, 1mmol) be dissolved in the methylene dichloride of 20mL, drip subsequently 10mL containing sodium ethylate (0.27g, dichloromethane solution 4mmol), stirring heating, back flow reaction 20 hours at 40 DEG C; 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 24.9%, reaction formula is as follows:
The Structural Identification result of compound P2 is as follows:
Mass spectrum (MS m/z): 1084.1 (M+)
Ultimate analysis: C
35h
17f
18irN
8
Theoretical value: C, 38.79; H, 1.58; F, 31.55; Ir, 17.74; N, 10.34
Measured value: C, 38.74; H, 1.66; F, 31.53; Ir, 17.71; N, 10.36
The end product P2 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-methylpyrimidine-N, C
4') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles) close complex of iridium.
At 298K temperature, P2 (～10
-6m) CH
2cl
2in solution, the maximum emission peak of emmission spectrum, at 435nm place, has an acromion at 465nm 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=0.10.
Embodiment 3
The present embodiment provides a kind of two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-tertiary butyl pyrimidine-N, C
4') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles) close complex of iridium, its chemical structure is as shown in P3:
The preparation process of above-mentioned P3 is as follows:
S10, Compound C 3(2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-tertiary butyl pyrimidine) synthetic
The compound A-13 (the bromo-5-tertiary butyl of 2-pyrimidine) 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 (1.08g, 5mmol), compd B (2.07g, 8mmol) and Pd (PPh
3)
4(0.11mg, 0.15mmol) is dissolved in the DMF of 25mL, then adds 10mL to contain the aqueous solution of sodium carbonate (2.12g, 20mmol), stirs 15 hours at 90 DEG C; 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 the sherwood oil that crude product is 1:8 by volume ratio again and the mixed solution of methylene dichloride are that eluent carries out silica gel column chromatography and separates, and obtains 0.49g Compound C 1 after dry, yield 28.1%, reaction formula is as follows:
The Structural Identification result of Compound C 3 is as follows:
Mass spectrum (MS m/z): 349.1 (M+)
Ultimate analysis: C
15h
13f
6n
3
Theoretical value: C, 51.58; H, 3.75; F, 32.64; N, 12.03
Measured value: C, 51.63; H, 3.66; F, 32.69; N, 12.02
The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-tertiary butyl pyrimidine;
S20's, compound d3 (part be 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-tertiary butyl pyrimidine containing iridium dichloro dimer) is synthetic
It is in the cellosolvo of 3:1 and the mixed solvent of water that Compound C 3 (0.87g, 2.5mmol) and three hydration iridous chlorides (0.36g, 1mmol) are dissolved in to 20mL volume ratio, and stirring reaction 24 hours refluxes at 100 DEG C; 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 0.21g after being dried, and yield is 22.7%, and reaction formula is as follows:
S30, P3(two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-tertiary butyl pyrimidine-N, C
4') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles) close complex of iridium) and synthetic
Compd E is as described in Example 1 provided;
Under nitrogen protection, by compound d3 (0.74g, 0.4mmol) and compd E (0.28g, 1mmol) be dissolved in the trichloromethane of 20mL, drip subsequently 10mL containing sodium ethylate (0.33g, chloroform soln 4.8mmol), is heated with stirring to 62 DEG C of back flow reaction 12 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 0.17g purifying through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 17.4%, reaction formula is as follows:
The Structural Identification result of compound P3 is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1224.2 (M+)
Ultimate analysis: C
45h
37f
18irN
8
Theoretical value: C, 44.16; H, 3.05; F, 27.94; Ir, 15.70; N, 9.15
Measured value: C, 44.12; H, 3.09; F, 27.88; Ir, 15.78; N, 9.13
The end product that the above-mentioned reaction of above data acknowledgement obtains is two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-5-tertiary butyl pyrimidine-N, C
4') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles) close complex of iridium.
At 298K temperature, P3 (～10
-6m) CH
2cl
2in solution, the maximum emission peak of emmission spectrum, at 441nm place, has an acromion at 472nm 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=0.15.
Embodiment 4
The present embodiment provides a kind of two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-4-eicosyl pyrimidine-N, C
4') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles) close complex of iridium, its chemical structure is as shown in P4:
The preparation process of above-mentioned P4 is as follows:
S10, Compound C 4(2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-4-eicosyl pyrimidine) synthetic
The bromo-4-eicosyl of the compd A 4(2-pyrimidine that provides following structural formula to represent) and compd B (2,6-bis-(trifluoromethyl) pyridine-3-boric acid):
Under nitrogen protection, by compound A-13 (2.20g, 5mmol), compd B (2.59g, 10mmol) and Pd (PPh
3)
2cl
2(0.21mg, 0.3mmol) is dissolved in the toluene of 30mL, then adds 20mL to contain the aqueous solution of salt of wormwood (1.38g, 10mmol), stirs 10 hours at 100 DEG C; 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 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 and separates, and obtains 0.37g Compound C 1 after dry, yield 12.9%, reaction formula is as follows:
The Structural Identification result of Compound C 4 is as follows:
Mass spectrum (MS m/z): 573.3 (M+)
Ultimate analysis: C
31h
45f
6n
3
Theoretical value: C, 64.90; H, 7.91; F, 19.87; N, 7.32
Measured value: C, 64.94; H, 7.82; F, 19.90; N, 7.34
The product C 4 that the above-mentioned reaction of above data acknowledgement obtains is 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-4-eicosyl pyrimidines;
S20, Compound D 4(part be 2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-4-eicosyl pyrimidine containing iridium dichloro dimer) synthetic
It is in the cellosolvo of 3:1 and the mixed solvent of water that Compound C 4 (0.57g, 1mmol) and three hydration iridous chlorides (0.18g, 0.5mmol) are dissolved in to 10mL volume ratio, and stirring reaction 24 hours refluxes at 100 DEG C; 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 4 of 0.09g after being dried, and yield is 13.1%, and reaction formula is as follows:
C4 D4 ；
S30, P4(two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-4-eicosyl pyrimidine-N, C
4') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles) close complex of iridium) and synthetic
Compd E is as described in Example 1 provided;
Under nitrogen protection, by Compound D 4 (0.82g, 0.3mmol) and compd E (0.25g, 0.9mmol) be dissolved in 1 of 20mL, in 2-ethylene dichloride, drip subsequently 10mL containing 1 of sodium methylate (0.16g, 3mmol), 2-dichloroethane solution, is heated with stirring to 84 DEG C 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 P4 that obtains 0.08g purifying through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 8.2%, reaction formula is as follows:
The Structural Identification result of compound P4 is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1616.7 (M+)
Ultimate analysis: C
73h
93f
18irN
8
Theoretical value: C, 54.23; H, 5.80; F, 21.15; Ir, 11.89; N, 6.93
Measured value: C, 54.27; H, 5.77; F, 21.11; Ir, 11.95; N, 6.90
The end product that the above-mentioned reaction of above data acknowledgement obtains is two (2-(2', 6'-bis-(trifluoromethyl) pyridine-3'-yl)-4-eicosyl pyrimidine-N, C
4') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles) close complex of iridium.
At 298K temperature, P3 (～10
-6m) CH
2cl
2in solution, the maximum emission peak of emmission spectrum, at 453nm 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=0.09.
Embodiment 5
The title complex P1 that the present embodiment provides taking the embodiment of the present invention 1 is the doping object of luminescent layer, prepare a kind of organic electroluminescence device, as shown in Figure 3, the structure of this organic electroluminescence device comprises the 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 that stack 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, on anode 301, preparing successively a layer thickness by vacuum evaporation 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, adopt 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.
Tested the electric current-brightness-voltage characteristic of above-mentioned organic electroluminescence device by Keithley source measuring system (Keithley2400Sourcemeter), 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 10.1%, and maximum lumen efficiency is 8.4lm/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 hydrogen atom or C
1～C
20alkyl.
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 hydrogen atom or C
1～C
20alkyl;
Under S20, protection of inert gas; described compd A and compd B are dissolved in by the mol ratio of 1:1～1:2 in the first organic solvent that contains palladium catalyst and alkali; obtain reaction solution; described reaction solution carried out Suzuki linked reaction after 8～15 hours at 85～100 DEG C; separation and purification reaction solution; obtain Compound C, its structural formula is as shown in C:
In formula, R is C
1～C
20alkyl;
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 DEG C 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 hydrogen atom or C
1～C
20alkyl;
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 by the mol ratio of 1:2～1:3 in the second organic solvent that contains sodium methylate or sodium ethylate; obtain mixing solutions; described mixing solutions carried out Suzuki linked reaction after 6～20 hours at 40～135 DEG C; separation and purification; obtain blue-ray organic electroluminescent material, its structural formula is as shown in P:
In formula, R is hydrogen atom or C
1～C
20alkyl.
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 0.1～0.2mol/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%～6% times; Described alkali is wet chemical or aqueous sodium carbonate, the mole dosage of described alkali is compd A 2～4 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, the sherwood oil that crude product is 1:5～1:8 by volume ratio again and methylene dichloride mixed solution are that eluent carries out silica gel column chromatography and separates, and 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 and 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, its structural formula is as shown in P:
In formula, R is hydrogen atom or C
1～C
20alkyl.
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Cited By (2)
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| CN105859789A (en) * | 2016-04-07 | 2016-08-17 | 瑞声光电科技(常州)有限公司 | Iridium complex and preparation method thereof, electroluminescent device using iridium complex |
| 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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