CN104177423A - Organic electroluminescent material, and preparation method and application thereof - Google Patents
Organic electroluminescent material, and preparation method and application thereof Download PDFInfo
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- CN104177423A CN104177423A CN201310193053.5A CN201310193053A CN104177423A CN 104177423 A CN104177423 A CN 104177423A CN 201310193053 A CN201310193053 A CN 201310193053A CN 104177423 A CN104177423 A CN 104177423A
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- 0 C*(*)(CNC)C=N Chemical compound C*(*)(CNC)C=N 0.000 description 1
- VRCGDNBLZUQJBK-UHFFFAOYSA-N FC(C1C=C(C(F)(F)F)NC1c1ccccn1)(F)F Chemical compound FC(C1C=C(C(F)(F)F)NC1c1ccccn1)(F)F VRCGDNBLZUQJBK-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention belongs to the field of photoelectric materials, and specifically relates to an organic electroluminescent material. A structural formula is shown in the description. In the formula, R represents alkyl of C1-C20. The 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 organic electroluminescent material also has relatively high phosphorescence quantum efficiency, relatively good solubility and processability. The invention also provides a preparation method of the organic electroluminescent material, and an application of the 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 electroluminescent organic 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 the OLED device of making of FIrpic 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 iridium metal complex two [2-(4', 6'-difluorophenyl) pyridine-N, C
2'] [2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles] close iridium (FIrfpy).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, the FIrfpy device of identity unit structure is compared with FIrpic device, and the blue light color purity of FIrfpy device is higher.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 blue-ray organic electroluminescent material of developing high color purity is still a large focus of OLED research field.
Summary of the invention
The invention provides a kind of electroluminescent organic material, this material has good blue light luminous efficiency and good processing characteristics.The preparation method that the present invention also provides this electroluminescent organic material with and application in organic electroluminescence device.
First aspect, the invention provides a kind of electroluminescent organic material, has following structural formula:
In formula, R is C
1～C
20alkyl.
This electroluminescent organic material is that a class is containing complex of iridium material, comprise cyclic metal complexes agent structure 2-(2', 6'-difluoro pyridine-3'-yl) pyrimidine and assistant ligand 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles.Pyrimidyl is conducive to improve the lumo energy of material, and two electron withdrawing group F bases on pyridyl and ring are conducive to reduce the HOMO energy level of material, make the effective blue shift of material emission wavelength.The difference of the electron-donating group alkoxyl group of the straight chain of different lengths or straight chain formula being introduced to pyrimidine ring replaces on position, the flexible side chain of the alkoxyl group of different lengths is conducive to increase its solvability in organic solvent on the one hand, and produce certain space steric effect, reduce the interaction force between material molecule, reduce the self-quenching phenomenon of triplet exciton; On the other hand, what alkoxyl group was stronger gives the further emission wavelength of blue shift material of electronic effect, therefore can obtain the blue light emitting wavelength that luminous efficiency is higher.Simultaneously, on phenyl ring 4, two fluorine-based F-of strong electron-withdrawing substituent of 6-position and high field intensity assistant ligand 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles's introducing blue shift emission wavelength effectively, different luminescent properties of joining type title complex can also be because intramolecular energy transfer be improved and improves, can reduce evaporation temperature, increase film forming properties and improve the stability of device.
Electroluminescent organic material provided by the invention can be used for the luminescent material of blue light or white-light electroluminescence device.
Second aspect, the invention provides a kind of preparation method of electroluminescent organic 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
20alkyl;
Under S20, protection of inert gas; described compd A and compd B are dissolved in by the mol ratio of 1:1～1:1.5 in the first organic solvent that contains palladium catalyst and alkali; obtain reaction solution; described reaction solution carries out Suzuki linked reaction after 10～15 hours under 80～90 ° of C; separation and purification reaction solution; obtain Compound C, its structural formula is as follows:
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 100 ° of C back flow reaction after 24 hours; be cooled to room temperature; separation and purification; obtain Compound D, its structural formula is as follows:
In formula, R is 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 carries out Suzuki linked reaction after 8～20 hours under 40～84 ° of C; separation and purification; obtain electroluminescent organic material, its structural formula is as follows:
In formula, R is C
1～C
20alkyl.
The reaction formula of step S20 is:
In formula, R is C
1～C
20alkyl.
Preferably, in step S20, palladium catalyst is that dichloro two (triphenylphosphine) is changed palladium (Pd (PPh
3)
2cl
2) or four (triphenylphosphines) close palladium (Pd (PPh
3)
4).
Preferably, alkali is wet chemical or aqueous sodium carbonate.
Preferably, the first organic solvent is DMF (DMF) or toluene.
Preferably, the volume ratio of the first organic solvent and wet chemical is 2:1～2.5:1.
Preferably, the volume ratio of the first organic solvent and aqueous sodium carbonate is 2:1～2.5:1.
Preferably, the concentration of compd A in reaction solution is 0.07～0.2mol/L, the mole dosage of palladium catalyst is compd A 0.03～0.05 times, the mole dosage of alkali is compd A 1～3 times.
Preferably, purification procedures in step S20 comprises: question response liquid is cooled to after room temperature, adopt dichloromethane extraction, then be washed with water to neutrality, after anhydrous magnesium sulfate drying, filter and obtain filtrate again, gained filtrate obtains crude product after removing desolventizing under reduced pressure, the ethyl acetate that crude product is 1:8 by volume ratio again and normal hexane mixed solution are that eluent carries out silica gel column chromatography and separates, and obtain Compound C.
The reaction formula of step S30 is:
In formula, R is C
1～C
20alkyl.
Preferably, the concentration of Compound C in reaction mixed solvent is 0.05～0.1mol/L.
Preferably, the purification procedures in step S30 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 Compound D.
The reaction formula of step S40 is:
In formula, R is C
1～C
20alkyl.
Preferably, the second organic solvent is 1,2-ethylene dichloride, methylene dichloride or trichloromethane.
Preferably, the concentration of Compound D in mixing solutions is 0.01～0.02mol/L, the mole dosage of sodium methylate or sodium ethylate is Compound D 8～12 times.
Preferably, the purification procedures in step S40 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 electroluminescent organic material.
The preparation method of a kind of electroluminescent organic material provided by the invention is simple, handled easily.
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 electroluminescent organic material providing as first aspect present invention, its structural formula is as follows:
In formula, R is C
1～C
20alkyl.
Organic electroluminescence device provided by the invention has good blue light emitting performance and stability.
A kind of electroluminescent organic material provided by the invention and its preparation method and application, its beneficial effect having is:
(1) electroluminescent organic material provided by the invention comprises cyclic metal complexes agent structure 2-(2', 6'-difluoro pyridine-3'-yl) pyrimidine and assistant ligand 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles.Pyrimidyl is conducive to improve the lumo energy of material, and two electron withdrawing group F bases on pyridyl and ring are conducive to reduce the HOMO energy level of material, make the effective blue shift of material emission wavelength.The difference of the electron-donating group alkoxyl group of the straight chain of different lengths or straight chain formula being introduced to pyrimidine ring replaces on position, produce certain space steric effect, reduce the interaction force between material molecule, reduce the self-quenching phenomenon of triplet exciton, obtain the higher blue light emitting wavelength of luminous efficiency;
(2) electroluminescent organic material provided by the invention, due to the introducing of different lengths oxyalkyl 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) electroluminescent organic 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 electroluminescent organic material that provides of the embodiment of the present invention 1;
Fig. 2 is the utilizing emitted light spectrogram of the electroluminescent organic 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, 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'-difluoro pyridine-3'-yl)-5-methoxy pyrimidine-N, C
4') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles) close complex of iridium, its chemical structural formula is as shown in P1:
The preparation process of above-mentioned P1 is as follows:
S10, the bromo-5-methoxy pyrimidine of the compd A 1(2-that provides following structural formula to represent) and compd B (2,6-difluoro pyridine-3-boric acid):
S20, Compound C 1(2-(2', 6'-difluoro pyridine-3'-yl)-5-methoxy pyrimidine) synthetic
Under nitrogen protection, by compd A 1 (1.89g, 10mmol), compd B (1.91g, 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), stirring reaction 10 hours under 90 ° of 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 ethyl acetate that crude product is 1:8 by volume ratio again and the mixed solution of normal hexane are that eluent carries out silica gel column chromatography and separates, and obtains 1.11g Compound C 1 after dry, yield is 49.7%, and reaction formula is as follows:
The Structural Identification result of Compound C 1 is as follows:
Mass spectrum (MS m/z): 223.1 (M
+)
Ultimate analysis: C
10h
7f
2n
3o
Theoretical value: C, 53.82; H, 3.16; F, 17.03; N, 18.83; O, 7.17
Measured value: C, 53.86; H, 3.10; F, 17.06; N, 18.80; O, 7.18
The product C 1 that the above-mentioned reaction of above data acknowledgement obtains is 2-(2', 6'-difluoro pyridine-3'-yl)-5-methoxy pyrimidine;
S30, Compound D 1(part be 2-(2', 6'-difluoro pyridine-3'-yl)-5-methoxy pyrimidine containing iridium dichloro dimer) synthetic
Under nitrogen protection, by Compound C 1 (0.89g, it is in the cellosolvo of 3:1 and the mixed solvent of water that 4mmol) He three hydration iridous chlorides (0.70g, 2mmol) are dissolved in 40mL volume ratio, and stirring reaction 24 hours refluxes under 100 ° of 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 0.61g after being dried, and yield is 43.9%, and reaction formula is as follows:
S40, P1(two (2-(2', 6'-difluoro pyridine-3'-yl)-5-methoxy 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 (0.70g, 0.5mmol) and compd E (0.35g, 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 C 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 0.30g purifying through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 32.8%, reaction formula is as follows:
The Structural Identification result of compound P1 is as follows:
Mass spectrum (MS m/z): 916.1 (M
+)
Ultimate analysis: C
31h
17f
10irN
8o
2
Theoretical value: C, 40.66; H, 1.87; F, 20.75; Ir, 20.99; N, 12.24; O, 3.49
Measured value: C, 40.68; H, 1.83; F, 20.78; Ir, 20.93; N, 12.28; O, 3.50
The product P 1 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(2', 6'-difluoro pyridine-3'-yl)-5-methoxy pyrimidine-N, C
4') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles) close complex of iridium.
Fig. 1 is the preparation flow schematic diagram of the electroluminescent organic material that provides of the embodiment of the present invention.
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 449nm place, has an acromion at 479nm place simultaneously, and P1 that this demonstration the present embodiment provides can be used as 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=0.15, 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'-difluoro pyridine-3'-yl)-4-hexyloxy pyrimidine-N, C
4') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles) close complex of iridium, its chemical structural formula is as shown in P2:
The preparation process of above-mentioned P2 is as follows:
S10, the bromo-4-hexyloxy of the compd A 2(2-pyrimidine that provides following structural formula to represent) and compd B (2,6-difluoro pyridine-3-boric acid):
S20, Compound C 2(2-(2', 6'-difluoro pyridine-3'-yl)-4-hexyloxy pyrimidine) synthetic
Under nitrogen protection, by compd A 2 (1.30g, 5mmol), compd B (0.79g, 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), under 80 ° of C, stirs 12 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 the ethyl acetate that crude product is 1:8 by volume ratio again and the mixed solution of normal hexane are that eluent carries out silica gel column chromatography and separates, and obtains 0.58g Compound C 2 after dry, yield is 39.5%, and reaction formula is as follows:
The Structural Identification result of Compound C 2 is as follows:
Mass spectrum (MS m/z): 293.1 (M
+)
Ultimate analysis: C
15h
17f
2n
3o
Theoretical value: C, 61.42; H, 5.84; F, 12.95; N, 14.33; O, 5.45
Measured value: C, 61.45; H, 5.80; F, 12.97; N, 14.31; O, 5.47
The product C 2 that the above-mentioned reaction of above data acknowledgement obtains is 2-(2', 6'-difluoro pyridine-3'-yl)-4-hexyloxy pyrimidines.
S30, Compound D 2(part be 2-(2', 6'-difluoro pyridine-3'-yl)-4-hexyloxy pyrimidine containing iridium dichloro dimer) synthetic
Under nitrogen protection, by Compound C 2 (0.64g, it is in the cellosolvo of 3:1 and the mixed solvent of water that 2.2mmol) He three hydration iridous chlorides (0.36g, 1mmol) are dissolved in 25mL volume ratio, and stirring reaction 24 hours refluxes under 100 ° of 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 0.15g after being dried, and yield is 18.5%, and reaction formula is as follows:
S40, P2(two (2-(2', 6'-difluoro pyridine-3'-yl)-4-hexyloxy 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 2 (0.65g, 0.4mmol) and compd E (0.22g, 0.8mmol) be dissolved in the methylene dichloride of 15mL, drip subsequently 10mL containing sodium ethylate (0.22g, dichloromethane solution 3.2mmol), stirring heating, back flow reaction 20 hours under 40 ° of 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 0.15g purifying through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 17.7%, reaction formula is as follows:
The Structural Identification result of compound P2 is as follows:
Mass spectrum (MS m/z): 1056.2 (M
+)
Ultimate analysis: C
41h
37f
10irN
8o
2
Theoretical value: C, 46.63; H, 3.53; F, 17.99; Ir, 18.20; N, 10.61; O, 3.03
Measured value: C, 46.66; H, 3.48; F, 18.04; Ir, 18.17; N, 10.64; O, 3.01
The product P 2 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(2', 6'-difluoro pyridine-3'-yl)-4-hexyloxy pyrimidine-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 455nm place, has an acromion at 484nm 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=0.08.
Embodiment 3
The present embodiment provides a kind of two (2-(2', 6'-difluoro pyridine-3'-yl)-5-eicosane oxygen yl pyrimidines-N, C
4') (2,4-bis-(trifluoromethyl)-5-(pyridine-2'-yl) pyrroles) close complex of iridium, its chemical structural formula is as shown in P3:
The preparation process of above-mentioned P3 is as follows:
S10, the compound A-13 (the bromo-5-eicosane of 2-oxygen yl pyrimidines) and the compd B (2,6-difluoro pyridine-3-boric acid) that provide following structural formula to represent:
S20, Compound C 3(2-(2', 6'-difluoro pyridine-3'-yl)-5-eicosane oxygen yl pyrimidines) synthetic
Under nitrogen protection, by compound A-13 (0.91g, 2mmol), compd B (0.48g, 3mmol) He four (triphenyl phosphorus) close in the toluene that palladium (0.07mg, 0.06mmol) is dissolved in 20mL, then add 10mL to contain sodium carbonate (0.21g, aqueous solution 2mmol) stirs 15 hours under 90 ° of 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 ethyl acetate that crude product is 1:8 by volume ratio again and the mixed solution of normal hexane are that eluent carries out silica gel column chromatography and separates, and obtains 0.10g Compound C 3 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): 489.3 (M
+)
Ultimate analysis: C
29h
45f
2n
3o
Theoretical value: C, 71.13; H, 9.26; F, 7.76; N, 8.58; O, 3.27
Measured value: C, 71.18; H, 9.20; F, 7.78; N, 8.55; O, 3.29
The C3 that the above-mentioned reaction of above data acknowledgement obtains is 2-(2', 6'-difluoro pyridine-3'-yl)-5-eicosane oxygen yl pyrimidines;
S30's, compound d3 (part be 2-(2', 6'-difluoro pyridine-3'-yl)-5-eicosane oxygen yl pyrimidines containing iridium dichloro dimer) is synthetic
Under nitrogen protection, by Compound C 3 (0.73g, it is in the cellosolvo of 3:1 and the mixed solvent of water that 1.5mmol) He three hydration iridous chlorides (0.18g, 0.5mmol) are dissolved in 30mL volume ratio, and stirring reaction 24 hours refluxes under 100 ° of 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 0.07g after being dried, and yield is 13.9%, and reaction formula is as follows:
S40, P3(two (2-(2', 6'-difluoro pyridine-3'-yl)-5-eicosane oxygen yl pyrimidines-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 (0.60g, 0.3mmol) and compd E (0.25g, 0.9mmol) be dissolved in the trichloromethane of 20mL, drip subsequently 10mL containing sodium methylate (0.19g, chloroform soln 3.6mmol), is heated with stirring to 62 ° of C 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, then 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 9.2%, reaction formula is as follows:
The Structural Identification result of compound P3 is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1448.7 (M
+)
Ultimate analysis: C
69h
93f
10irN
8o
2
Theoretical value: C, 57.20; H, 6.47; F, 13.11; Ir, 13.27; N, 7.73; O, 2.21
Measured value: C, 57.26; H, 6.42; F, 13.07; Ir, 13.32; N, 7.70; O, 2.23
The product P 3 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(2', 6'-difluoro pyridine-3'-yl)-5-eicosane oxygen yl pyrimidines-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 470nm place, has an acromion at 500nm 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 P3
pL=0.04.
Embodiment 4
The title complex P1 that the present embodiment provides taking the embodiment of the present invention 1 is the doping object of luminescent layer, be prepared with organic electroluminescence devices, 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 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 6.6%, and maximum lumen efficiency is 7.0lm/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. an electroluminescent organic material, is characterized in that, has following structural formula:
In formula, R is C
1～C
20alkyl.
2. a preparation method for electroluminescent organic 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
20alkyl;
Under S20, protection of inert gas; described compd A and compd B are dissolved in by the mol ratio of 1:1～1:1.5 in the first organic solvent that contains palladium catalyst and alkali; obtain reaction solution; described reaction solution carries out Suzuki linked reaction after 10～15 hours under 80～90 ° of C; separation and purification reaction solution; obtain Compound C, its structural formula is as follows:
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 100 ° of C back flow reaction after 24 hours; be cooled to room temperature; separation and purification; obtain Compound D, its structural formula is as follows:
In formula, R is 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 carries out Suzuki linked reaction after 8～20 hours under 40～84 ° of C; separation and purification; obtain electroluminescent organic material, its structural formula is as follows:
In formula, R is C
1～C
20alkyl.
3. the preparation method of electroluminescent organic 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 electroluminescent organic 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 0.03～0.05 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 electroluminescent organic material as claimed in claim 2, it is characterized in that, in described S20, described purification procedures comprises: question response liquid 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 ethyl acetate that crude product is 1:8 by volume ratio again and normal hexane mixed solution are that eluent carries out silica gel column chromatography and separates, and obtain described Compound C.
6. the preparation method of electroluminescent organic 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 electroluminescent organic 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 electroluminescent organic 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 described Compound D 8～12 times.
9. the preparation method of electroluminescent organic 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 electroluminescent organic material.
10. an organic electroluminescence device, comprises luminescent layer, it is characterized in that, in described luminescent layer, doped with electroluminescent organic material as claimed in claim 1, its structural formula is as follows:
In formula, R is C
1～C
20alkyl.
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