CN104327828A - Blue ray organic electroluminescent material and preparation method and application thereof - Google Patents

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 or C1-C20 alkoxy. 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

A kind of blue-ray organic electroluminescent material and its preparation method and application

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 by the restriction of spin statistics theory, 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 hot research direction in after this this field.The title complex of iridium, ruthenium, platinum etc. can obtain very high emitted energy from the triplet state of self, and wherein metal iridium (III) compound, due to good stability, in building-up process, reaction conditions is gentle, and there is very high electroluminescent properties, in research process subsequently, account 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-pyridinecarboxylic) close iridium (FIrpic) (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 FIrpic the blue light sent out be sky blue, blue light color purity is not good enough, the CIE of each OLED made is (0.13 ~ 0.17, 0.29 ~ 0.39) change between, 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'-base) pyrroles] close iridium (FIrfpy) (J.Mater.Chem., 2007, 17, 1692-1698), FIrfpy is a kind of with 2, 4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles is the blue light organic phosphorescent electroluminescent materials of 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, the introducing of 4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles is the blue shift emission wavelength of material effectively, thus improve blue light color purity, this makes 2,4-bis-(trifluoromethyl)-5-(pyridine-2'-base) pyrroles become one of first-selected assistant ligand of different distribution type blue phosphorescent complex of iridium luminescent material.

2008, the Jun Yeob Lee teach problem group of Tan Guo university of Korea S reports three (2-(4', the fluoro-5'-cyano-phenyl of 6'-bis-) pyridine-N, C2') iridium (FCNIr) novel blue light phosphor material is closed, compared with Firpic, FCNIr cyclic metal complexes agent structure introduces strong electron-withdrawing group group cyano group, the HOMO energy level of FCNIr material is declined, emission wavelength blue shift, the maximum emission wavelength of the blue emitting phosphor device PHOLEDs made of it is blue shifted to 453nm, purity of color CIEx, y are also increased to (0.15,0.19);

In addition, within 2011, Jun Yeob Lee teach problem group reports blue emitting phosphor material---two (2-(4' of cyano-containing in another kind of ring master metal part, the fluoro-5'-cyano-phenyl of 6'-bis-) pyridine-N, C2') (2-pyridinecarboxylic) closes iridium (FCNIrpic), research finds, the excellent performance that FCNIrpic shows in blue light and white light parts, by optimised devices structure, the maximum emission wavelength of FCNIrpic blue-light device is blue shifted to 457 ~ 462nm, purity of color CIEx, y is also increased to (0.14 ~ 0.18,0.17 ~ 0.25); Facts have proved, in the main part of phosphor material complex of iridium, introduce strong electron-withdrawing substituent-cyano group is one of effective ways obtaining novel blue light with high color purity phosphor material.

In order to make device obtain full-color display, generally must obtain the ruddiness of excellent performance, green glow and blue light material simultaneously.Generally speaking, the development of blue phosphor materials lags behind ruddiness and green glow.So the blue-ray organic electroluminescent material developing high color purity and high-luminous-efficiency is still a large focus of OLED research field.

Summary of the invention

For solving the problem, the invention provides a kind of blue-ray organic electroluminescent material, this material has good blue light luminous efficiency and good processing characteristics.Present invention also offers the preparation method of this blue-ray organic electroluminescent material and its application in organic electroluminescence device.

First aspect, the invention provides a kind of blue-ray organic electroluminescent material, structural formula is as shown in P:

In formula, R is hydrogen atom, C ₁~ C ₂₀alkyl or 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 is containing complex of iridium material, comprise cyclic metal complexes agent structure 2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl) and pyrimidine and assistant ligand 2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles, from luminous efficiency: described cyclic metal complexes agent structure, pyrimidyl is the N heterocycle of high lumo energy, electrophilic cyano group on phenyl ring and two fluorine-based HOMO energy levels that can reduce material of electrophilic, be conducive to effective blue shift of material emission wavelength, secondly, on pyrimidine ring, the electro mass-energy of giving of alkyl or alkoxyl group improves the blue light emitting performance of material further, on the other hand, the introducing of this alkyl or alkoxyl group can produce certain space steric effect, thus the self-quenching phenomenon of 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 '-Ji) pyrroles can make the more acceptant electronics of material, thus improve the luminous efficiency of material further, angle from materials processing: pyrimidine ring, the alkyl of different lengths or oxyalkyl chain can increase material solvability in organic solvent, different distribution type title complex can reduce evaporation temperature, increase film-forming properties, thus improve Drawing abillity and improve the stability of device.

Second aspect, the invention provides a kind of preparation method of blue-ray organic electroluminescent material, comprises the steps:

S10, the compd A providing following structural formula to represent and compd B:

In formula, R is hydrogen atom, C ₁~ C ₂₀alkyl or C ₁~ C ₂₀alkoxyl group;

Under S20, protection of inert gas; described compd A and compd B are dissolved in the first organic solvent containing palladium catalyst and alkali by the mol ratio of 1:1 ~ 1:1.5; obtain reaction solution; described reaction solution carries out Suzuki linked reaction after 6 ~ 12 hours at 80 ~ 100 DEG C; separation and purification reaction solution; obtain Compound C, its structural formula as shown at c:

In formula, R is hydrogen atom, C ₁~ C ₂₀alkyl or 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 hydrated iridium trichloride are dissolved in volume ratio by the mol ratio of 2:1 ~ 4:1; be heated to reflux state stirring reaction subsequently after 24 hours; be cooled to room temperature; separation and purification; obtain Compound D, its structural formula as shown atd:

In formula, R is hydrogen atom, C ₁~ C ₂₀alkyl or C ₁~ C ₂₀alkoxyl group;

S40, the compd E providing following structural formula to represent:

Under protection of inert gas; described Compound D and compd E are dissolved in the second organic solvent containing sodium carbonate or salt of wormwood by the mol ratio of 1:2 ~ 1:3; obtain mixing solutions; described mixing solutions carried out Suzuki linked reaction after 5 ~ 10 hours at 84 ~ 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, C ₁~ C ₂₀alkyl or C ₁~ C ₂₀alkoxyl group.

Preferably, in described S20, the concentration of described compd A in reaction solution is 0.1 ~ 0.2mol/L; Described first organic solvent is DMF (DMF) or toluene.

Preferably, in described S20, the volume ratio of described first organic solvent and wet chemical is about 2:1.

Preferably, in described S20, the volume ratio of described first organic solvent and aqueous sodium carbonate is about 2:1.

Preferably, in described S20, described palladium catalyst is that dichloro two (triphenylphosphine) changes palladium or four (triphenylphosphines) close palladium, and the mole dosage of described palladium catalyst is 2% ~ 5% times of compd A; Described alkali is wet chemical or aqueous sodium carbonate, and the mole dosage of described alkali is 1 ~ 3 times of compd A.

Preferably, in described S20, described purification procedures comprises: after reaction solution is cooled to 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 to be ethyl acetate and the normal hexane mixed solution of 1:5 ~ 1:10 be crude product volume ratio that eluent carries out silica gel column chromatography is separated, and obtains described Compound C.

Preferably, in described S30, the concentration of described Compound C in reaction system is 0.1 ~ 0.2mol/L.

Preferably, in described S30, described purification procedures comprises: after question response stopping is chilled to room temperature, rotates and steam except partial solvent, add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, obtains described Compound D after drying.

Preferably, in described S40, described second organic solvent is 2-methyl cellosolve or cellosolvo.

Preferably, in described S40, the concentration of described Compound D in mixing solutions is 0.01 ~ 0.02mol/L, and the mole dosage of described sodium methylate or sodium ethylate is 8 ~ 12 times of Compound D.

Preferably, in described S40, described purification procedures comprises: after question response stops being chilled to room temperature, and concentrated remove portion solvent, adds appropriate distilled water, have solid to separate out; Collecting by filtration 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, obtains 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 compd A 1, A2, A3, A4 respectively 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, present invention also offers a kind of organic electroluminescence device, comprises luminescent layer, and doped with blue-ray organic electroluminescent material as described in relation to the first aspect in described luminescent layer, its structural formula is as shown in P:

In formula, R is hydrogen atom, C ₁~ C ₂₀alkyl or C ₁~ C ₂₀alkoxyl group.

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, and device can be made to have good blue light emitting performance; In addition, this material filming performance is good, easily processes.

A kind of blue-ray organic electroluminescent material provided by the invention and its preparation method and application, its beneficial effect had is:

(1) blue-ray organic electroluminescent material provided by the invention comprises cyclic metal complexes agent structure 2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl) and pyrimidine and assistant ligand 2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles, in described cyclic metal complexes agent structure, pyrimidyl is the N heterocycle of high lumo energy, electrophilic cyano group on phenyl ring and two electrophilics fluorine-based, be conducive to reducing the HOMO energy level of material, thus make the effective blue shift of the emission wavelength of material, secondly, on pyrimidine ring, the electro mass-energy of giving of alkyl or alkoxyl group improves the blue light emitting performance of material further, on the other hand, the introducing of this alkyl or alkoxyl group can produce certain space steric effect, thus the self-quenching phenomenon of 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 '-Ji) pyrroles can make the more acceptant electronics of material, thus improve the luminous efficiency of material further,

(2) blue-ray organic electroluminescent material provided by the invention, due to the introducing of different lengths alkyl chain or oxyalkyl chain on pyrimidine ring, improve material solubility property in organic solvent, different distribution type title complex can reduce evaporation temperature, the film forming properties of material can be increased, thus 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 the embodiment of the present invention 1 provides;

Fig. 2 is the utilizing emitted light spectrogram of the blue-ray organic electroluminescent material that the embodiment of the present invention 1 provides;

Fig. 3 is the structural representation of the organic electroluminescence device that the embodiment of the present invention 5 provides.

Embodiment

Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.

Embodiment 1

The preparation flow schematic diagram of the blue-ray organic electroluminescent material shown in composition graphs 1, present embodiments provides a kind of two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl) pyrimidine-N, C ^2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) 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-(3 ', 5 '-two fluoro-4 '-cyano-phenyl) pyrimidine) synthesis

The compd A 1(2-bromo pyrimi piperidine providing following structural formula to represent) and compd B (the fluoro-4-cyanophenylboronic acid of 3,5-bis-):

Under nitrogen protection, by compd A 1 (1.59g, 10mmol), compd B (2.20g, 12mmol) and Pd (PPh ₃) ₄(0.58mg, 0.5mmol) is dissolved in the toluene of 40mL, then adds the aqueous solution of 20mL containing salt of wormwood (2.76g, 20mmol), stirring reaction 6 hours at 100 DEG C; After question response liquid cooling to room temperature, with dichloromethane extraction, separatory, then neutrality is washed to, filter with after anhydrous magnesium sulfate drying again, filtrate obtains crude product through removing desolventizing under reduced pressure, and to be the ethyl acetate of 1:10 again by volume ratio with the mixed solution of normal hexane be crude product that eluent carries out silica gel column chromatography is separated, and obtains 1.06g Compound C 1 after drying, yield is 48.8%, and reaction formula is as follows:

The Structural Identification result of Compound C 1 is as follows:

Mass spectrum (MS m/z): 217.0 (M+)

Ultimate analysis: C ₁₁h ₅f ₂n ₃

Theoretical value: C, 60.83; H, 2.32; F, 17.50; N, 19.35

Measured value: C, 60.87; H, 2.25; F, 17.57; N, 19.31

The product C 1 that the above-mentioned reaction of above data acknowledgement obtains is 2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl) pyrimidine;

S20, Compound D 1(part be 2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl) pyrimidine containing iridium dichloro dimer) synthesis

Under nitrogen protection, by Compound C 1 (0.54g, it is, in the cellosolvo of 3:1 and the mixed solvent of water, be heated to reflux state stirring reaction 24 hours that 2.5mmol) He three hydrated iridium trichloride (0.35g, 1mmol) are dissolved in 20mL volume ratio; After being chilled to room temperature, rotating and steam except partial solvent, then add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, and obtain the Compound D 1 of 0.37g after drying, yield is 56.1%, and reaction formula is as follows:

S30, P1(two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl) pyrimidine-N, C ^2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close complex of iridium) synthesis

The compd E that theres is provided following structural formula to represent (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles):

Under nitrogen protection, Compound D 1 (0.66g, 0.5mmol) and compd E (0.34g, 1.2mmol) are dissolved in 25mL containing sodium carbonate (0.53g, in cellosolvo 5mmol), be heated with stirring to 135 DEG C of reflux states and react 6 hours; Naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, there is solid to separate out, filter, collect crude product, crude product uses deionized water, methanol wash for several times successively, obtain the P1 of 0.27g purifying through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 29.9%, and reaction formula is as follows:

The Structural Identification result of compound P1 is as follows:

Mass spectrum (MS m/z): 904.1 (M+)

Ultimate analysis: C ₃₃h ₁₃f ₁₀irN ₈

Theoretical value: C, 43.86; H, 1.45; F, 21.02; Ir, 21.27; N, 12.40

Measured value: C, 43.83; H, 1.51; F, 21.06; Ir, 21.14; N, 12.46

The product P 1 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl) pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close complex of iridium.

As shown in Figure 2, transverse axis is wavelength (Wavelength, unit nm), 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 462nm place, has an acromion at 486nm place simultaneously, and the P1 that this display 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 at 298K temperature, with the CH of the FIrpic under the same terms ₂cl ₂solution is standard (Φ _pL=0.26) Φ of P1, is recorded _pL=0.20, the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency.

Embodiment 2

Present embodiments provide a kind of two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-methylpyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) 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-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-methylpyrimidine) synthesis

The compd A 2(2-bromo-5-methylpyrimidine providing following structural formula to represent) and compd B (the fluoro-4-cyanophenylboronic acid of 3,5-bis-):

Under nitrogen protection, by compd A 2 (1.73g, 10mmol), compd B (1.83g, 10mmol) and Pd (PPh ₃) ₂cl ₂(0.28mg, 0.4mmol) is dissolved in the DMF of 50mL, then adds the aqueous solution of 25mL containing sodium carbonate (3.18g, 30mmol), stirs 8 hours at 90 DEG C; After question response liquid cooling to room temperature, with dichloromethane extraction, separatory, then neutrality is washed to, filter with after anhydrous magnesium sulfate drying again, filtrate obtains crude product through removing desolventizing under reduced pressure, and to be the sherwood oil of 1:8 again by volume ratio with the mixed solution of methylene dichloride be crude product that eluent carries out silica gel column chromatography is separated, and obtains 0.88g Compound C 1 after drying, yield is 38.1%, and reaction formula is as follows:

The Structural Identification result of Compound C 2 is as follows:

Mass spectrum (MS m/z): 231.1 (M+)

Ultimate analysis: C ₁₂h ₇f ₂n ₃

Theoretical value: C, 62.34; H, 3.05; F, 16.43; N, 18.17

Measured value: C, 62.38; H, 3.01; F, 16.49; N, 18.12

The product C 2 that the above-mentioned reaction of above data acknowledgement obtains is 2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-4-methylpyrimidines.

S20, Compound D 2(part be 2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-4-methylpyrimidine containing iridium dichloro dimer) synthesis

Compound C 2 (0.42g, 2mmol) and three hydrated iridium trichloride (0.35g, 1mmol) being dissolved in 20mL volume ratio is, in the cellosolvo of 3:1 and the mixed solvent of water, be heated to reflux state stirring reaction 24 hours; After being chilled to room temperature, rotating and steam except partial solvent, then add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, and obtain the Compound D 2 of 0.28g after drying, yield is 40.7%, and reaction formula is as follows:

S30, P2(two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-4-methylpyrimidine-N, C ^2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close complex of iridium) synthesis

Compd E is as described in Example 1 provided;

Under nitrogen protection, by Compound D 2 (0.69g, 0.5mmol) and compd E (0.28g, 1mmol) be dissolved in 30mL containing salt of wormwood (0.55g, in 2-methyl cellosolve 4mmol), stirring heating, back flow reaction 20 hours at 40 DEG C; Naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, there is solid to separate out, filter, collect crude product, crude product uses deionized water, methanol wash for several times successively, obtain the P2 of 0.23g purifying through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 24.7%, and reaction formula is as follows:

The Structural Identification result of compound P2 is as follows:

Mass spectrum (MS m/z): 932.1 (M+)

Ultimate analysis: C ₂₈h ₁₂f ₄irN ₁₁

Theoretical value: C, 45.12; H, 1.84; F, 20.39; Ir, 20.63; N, 12.03

Measured value: C, 45.18; H, 1.77; F, 20.42; Ir, 20.58; N, 12.05

The product P 2 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-4-methylpyrimidine-N, C ^2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close complex of iridium.

At 298K temperature, P2 (~ 10 ^-6m) CH ₂cl ₂in solution, the maximum emission peak of emmission spectrum is at 460nm place, has an acromion at 485nm place simultaneously; In addition, 10 ^-6the CH of M product P 2 ₂cl ₂solution at 298K temperature, with the CH of the FIrpic under the same terms ₂cl ₂solution is standard (Φ _pL=0.26) Φ of P2, is recorded _pL=0.08.

Embodiment 3

Present embodiments provide a kind of two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-t-butyl pyrimidines-N, C ^2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) 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-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-t-butyl pyrimidines) synthesis

The compound A-13 (2-bromo-5-t-butyl pyrimidines) providing following structural formula to represent and compd B (the fluoro-4-cyanophenylboronic acid of 3,5-bis-):

Under nitrogen protection, by compound A-13 (2.15g, 10mmol), compd B (2.56g, 14mmol) and Pd (PPh ₃) ₂cl ₂(0.21mg, 0.3mmol) is dissolved in the DMF of 35mL, then adds the aqueous solution of 15mL containing sodium carbonate (1.06g, 10mmol), stirs 10 hours at 85 DEG C; After question response liquid cooling to room temperature, with dichloromethane extraction, separatory, then neutrality is washed to, filter with after anhydrous magnesium sulfate drying again, filtrate obtains crude product through removing desolventizing under reduced pressure, and to be the ethyl acetate of 1:6 again by volume ratio with the mixed solution of normal hexane be crude product that eluent carries out silica gel column chromatography is separated, and obtains 0.82g Compound C 3 after drying, yield 30.0%, reaction formula is as follows:

The Structural Identification result of Compound C 3 is as follows:

Mass spectrum (MS m/z): 273.1 (M+)

Ultimate analysis: C ₁₅h ₁₃f ₂n ₃

Theoretical value: C, 65.93; H, 4.79; F, 13.90; N, 15.38

Measured value: C, 65.87; H, 4.84; F, 13.93; N, 15.36

The C3 that the above-mentioned reaction of above data acknowledgement obtains is 2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-t-butyl pyrimidines;

The synthesis of S20, compound d3 (part be 2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-t-butyl pyrimidines containing iridium dichloro dimer)

Compound C 3 (0.82g, 3mmol) and three hydrated iridium trichloride (0.35g, 1mmol) being dissolved in 20mL volume ratio is, in the cellosolvo of 3:1 and the mixed solvent of water, be heated to reflux state stirring reaction 24 hours; After being chilled to room temperature, rotating and steam except partial solvent, then add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, and obtain the compound d3 of 0.25g after drying, yield is 32.4%, and reaction formula is as follows:

S30, P3(two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-t-butyl pyrimidines-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close complex of iridium) and synthesis

Compd E as described in Example 1 is provided;

Under nitrogen protection, compound d3 (0.62g, 0.4mmol) and compd E (0.28g, 1mmol) are dissolved in 30mL containing sodium carbonate (0.51g, in cellosolvo 4.8mmol), be heated with stirring to 90 DEG C of back flow reaction 9 hours; Naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, there is solid to separate out, filter, collect crude product, crude product uses deionized water, methanol wash for several times successively, obtain the P3 of 0.12g purifying through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 14.8%, and reaction formula is as follows:

The Structural Identification result of compound P3 is as follows:

Structural Identification:

Mass spectrum (MS m/z): 1016.2 (M+)

Ultimate analysis: C ₄₁h ₂₉f ₁₀irN ₈

Theoretical value: C, 48.47; H, 2.88; F, 18.70; Ir, 18.92; N, 11.03

Measured value: C, 48.53; H, 2.80; F, 18.75; Ir, 18.87; N, 11.05

The product P 3 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-t-butyl pyrimidines-N, C ^2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close complex of iridium.

At 298K temperature, P3 (~ 10 ^-6m) CH ₂cl ₂in solution, the maximum emission peak of emmission spectrum is at 469nm place, has an acromion at 497nm place simultaneously; In addition, 10 ^-6the CH of M product P 3 ₂cl ₂solution at 298K temperature, with the CH of the FIrpic under the same terms ₂cl ₂solution is standard (Φ _pL=0.26) Φ of P2, is recorded _pL=0.14.

Embodiment 4

Present embodiments provide a kind of two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-4-eicosyl pyrimidine-N, C ^2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) 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-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-4-eicosyl pyrimidine) synthesis

The compd A 4(2-bromo-4-eicosyl pyrimidine providing following structural formula to represent) and compd B (the fluoro-4-cyanophenylboronic acid of 3,5-bis-):

Under nitrogen protection, by compd A 4 (2.20g, 5mmol), compd B (1.37g, 7.5mmol) and Pd (PPh ₃) ₄(0.12mg, 0.1mmol) is dissolved in the toluene of 35mL, then adds the aqueous solution of 15mL containing salt of wormwood (1.73g, 12.5mmol), stirs 12 hours at 85 DEG C; After question response liquid cooling to room temperature, with dichloromethane extraction, separatory, then neutrality is washed to, filter with after anhydrous magnesium sulfate drying again, filtrate obtains crude product through removing desolventizing under reduced pressure, and to be the ethyl acetate of 1:5 again by volume ratio with the mixed solution of normal hexane be crude product that eluent carries out silica gel column chromatography is separated, and obtains 0.45g Compound C 4 after drying, yield 18.1%, reaction formula is as follows:

The Structural Identification result of Compound C 4 is as follows:

Mass spectrum (MS m/z): 497.4 (M+)

Ultimate analysis: C ₃₁h ₄₅f ₂n ₃

Theoretical value: C, 74.81; H, 9.11; F, 7.63; N, 8.44

Measured value: C, 74.87; H, 9.03; F, 7.68; N, 8.42

The C4 that the above-mentioned reaction of above data acknowledgement obtains is 2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-4-eicosyl pyrimidine;

S20, Compound D 4(part be 2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-4-eicosyl pyrimidine containing iridium dichloro dimer) synthesis

Compound C 4 (0.99g, 2mmol) and three hydrated iridium trichloride (0.18g, 0.5mmol) being dissolved in 10mL volume ratio is, in the cellosolvo of 3:1 and the mixed solvent of water, be heated to reflux state stirring reaction 24 hours; After being chilled to room temperature, rotating and steam except partial solvent, then add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, and obtain the Compound D 4 of 0.09g after drying, yield is 14.7%, and reaction formula is as follows:

S30, P4(two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-4-eicosyl pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close complex of iridium) and synthesis

Compd E as described in Example 1 is provided;

Under nitrogen protection, Compound D 4 (0.73g, 0.3mmol) and compd E (0.25g, 0.9mmol) are dissolved in 30mL containing salt of wormwood (0.40g, in 2-methyl cellosolve 3mmol), be heated with stirring to 84 DEG C of back flow reaction 10 hours; Naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, there is solid to separate out, filter, collect crude product, crude product uses deionized water, methanol wash for several times successively, obtain the P4 of 0.04g purifying through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 4.5%, and reaction formula is as follows:

The Structural Identification result of compound P4 is as follows:

Structural Identification:

Mass spectrum (MS m/z): 1464.7 (M+)

Ultimate analysis: C ₇₃h ₉₃f ₁₀irN ₈

Theoretical value: C, 59.86; H, 6.40; F, 12.97; Ir, 13.12; N, 7.65

Measured value: C, 59.83; H, 6.45; F, 12.91; Ir, 13.18; N, 7.63

The product P 4 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-4-eicosyl pyrimidine-N, C ^2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close complex of iridium.

At 298K temperature, P4 (~ 10 ^-6m) CH ₂cl ₂in solution, the maximum emission peak of emmission spectrum is at 487nm place, has an acromion at 512nm place simultaneously; In addition, 10 ^-6the CH of M product P 4 ₂cl ₂solution at 298K temperature, with the CH of the FIrpic under the same terms ₂cl ₂solution is standard (Φ _pL=0.26) Φ of P2, is recorded _pL=0.01.

Embodiment 5

Present embodiments provide a kind of two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-methoxy pyrimidine-N, C ^2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close complex of iridium, its chemical structure is as shown in P5:

The preparation process of above-mentioned P5 is as follows:

S10, Compound C 5(2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-methoxy pyrimidine) synthesis

The compound A-45 (2-bromo-5-methoxy pyrimidine) providing following structural formula to represent and compd B (the fluoro-4-cyanophenylboronic acid of 3,5-bis-):

Under nitrogen protection, by compound A-45 (1.89g, 10mmol), compd B (2.20g, 12mmol) and Pd (PPh ₃) ₄(0.58mg, 0.5mmol) is dissolved in the DMF of 35mL, then adds the aqueous solution of 15mL containing salt of wormwood (2.76g, 20mmol), stirring reaction 6 hours at 100 DEG C; After question response liquid cooling to room temperature, with dichloromethane extraction, separatory, then neutrality is washed to, filter with after anhydrous magnesium sulfate drying again, filtrate obtains crude product through removing desolventizing under reduced pressure, and to be the ethyl acetate of 1:7 again by volume ratio with the mixed solution of normal hexane be crude product that eluent carries out silica gel column chromatography is separated, and obtains 0.91g Compound C 5 after drying, yield is 36.8%, and reaction formula is as follows:

The Structural Identification result of Compound C 5 is as follows:

Mass spectrum (MS m/z): 247.1 (M+)

Ultimate analysis: C ₁₂h ₇f ₂n ₃o

Theoretical value: C, 58.30; H, 2.85; F, 15.37; N, 17.00; O, 6.47

Measured value: C, 58.36; H, 2.77; F, 15.40; N, 17.04; O, 6.43

The product C 5 that the above-mentioned reaction of above data acknowledgement obtains is 2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-methoxy pyrimidine;

S20, Compound D 5(part be 2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-methoxy pyrimidine containing iridium dichloro dimer) synthesis

Under nitrogen protection, by Compound C 5 (0.49g, it is, in the cellosolvo of 3:1 and the mixed solvent of water, be heated to reflux state stirring reaction 24 hours that 2mmol) He three hydrated iridium trichloride (0.35g, 1mmol) are dissolved in 20mL volume ratio; After being chilled to room temperature, rotating and steam except partial solvent, then add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, and obtain the Compound D 5 of 0.25g after drying, yield is 34.7%, and reaction formula is as follows:

S30, P5(two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-methoxy pyrimidine-N, C ^2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close complex of iridium) synthesis

The compd E that theres is provided following structural formula to represent (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles):

Under nitrogen protection, Compound D 5 (0.72g, 0.5mmol) and compd E (0.35g, 1.25mmol) are dissolved in 25mL containing sodium carbonate (0.53g, in cellosolvo 5mmol), be heated with stirring to 84 DEG C of reflux states and react 8 hours; Naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, there is solid to separate out, filter, collect crude product, crude product uses deionized water, methanol wash for several times successively, obtain the P5 of 0.23g purifying through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 23.9%, and reaction formula is as follows:

The Structural Identification result of compound P5 is as follows:

Mass spectrum (MS m/z): 964.1 (M+)

Ultimate analysis: C ₃₅h ₁₇f ₁₀irN ₈o ₂

Theoretical value: C, 43.62; H, 1.78; F, 19.71; Ir, 19.94; N, 11.63; O, 3.32

Measured value: C, 43.55; H, 1.86; F, 19.67; Ir, 19.98; N, 11.60; O, 3.34

The product P 5 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-methoxy pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close complex of iridium.

As shown in Figure 2, transverse axis is wavelength (Wavelength, unit nm), and the longitudinal axis is standardized photoluminescence intensity (Normalized PL intensity), at 298K temperature, and P5 (~ 10 ^-6m) at CH ₂cl ₂in solution, the maximum emission peak of emmission spectrum is at 461nm place, has an acromion at 485nm place simultaneously, and the P5 that this display 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 5 (~ 10 ^-6m) CH ₂cl ₂solution at 298K temperature, with the CH of the FIrpic under the same terms ₂cl ₂solution is standard (Φ _pL=0.26) Φ of P5, is recorded _pL=0.09, the iridium electroluminescent organic material that contains of visible the present embodiment has higher luminous quantum efficiency.

Embodiment 6

Present embodiments provide a kind of two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-4-hexyloxy pyrimidine-N, C ²') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close complex of iridium, its chemical structure is as shown in P6:

The preparation process of above-mentioned P6 is as follows:

S10, Compound C 6(2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-4-hexyloxy pyrimidine) synthesis

The compd A 6(2-bromo-4-hexyloxy pyrimidine providing following structural formula to represent) and compd B (the fluoro-4-cyanophenylboronic acid of 3,5-bis-):

Under nitrogen protection, by compd A 6 (2.59g, 10mmol), compd B (1.83g, 10mmol) and Pd (PPh ₃) ₂cl ₂(0.21mg, 0.3mmol) is dissolved in the DMF of 40mL, then adds the aqueous solution of 20mL containing sodium carbonate (1.06g, 10mmol), stirs 10 hours at 80 DEG C; After question response liquid cooling to room temperature, with dichloromethane extraction, separatory, then neutrality is washed to, filter with after anhydrous magnesium sulfate drying again, filtrate obtains crude product through removing desolventizing under reduced pressure, and to be the sherwood oil of 1:10 again by volume ratio with the mixed solution of methylene dichloride be crude product that eluent carries out silica gel column chromatography is separated, and obtains 0.92g Compound C 6 after drying, yield is 29.0%, and reaction formula is as follows:

The Structural Identification result of Compound C 6 is as follows:

Mass spectrum (MS m/z): 317.1 (M+)

Ultimate analysis: C ₁₇h ₁₇f ₂n ₃o

Theoretical value: C, 64.34; H, 5.40; F, 11.97; N, 13.24; O, 5.04

Measured value: C, 64.39; H, 5.33; F, 12.04; N, 13.26; O, 4.98

The product C 6 that the above-mentioned reaction of above data acknowledgement obtains is 2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-4-hexyloxy pyrimidines.

S20, Compound D 6(part be 2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-4-hexyloxy pyrimidine containing iridium dichloro dimer) synthesis

Compound C 6 (0.95g, 3mmol) and three hydrated iridium trichloride (0.36g, 1mmol) being dissolved in 25mL volume ratio is, in the cellosolvo of 3:1 and the mixed solvent of water, be heated to reflux state stirring reaction 24 hours; After being chilled to room temperature, rotating and steam except partial solvent, then add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, and obtain the Compound D 6 of 0.22g after drying, yield is 25.6%, and reaction formula is as follows:

S30, P6(two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-4-hexyloxy pyrimidine-N, C ^2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close complex of iridium) synthesis

Compd E is as described in Example 1 provided;

Under nitrogen protection, by Compound D 6 (0.69g, 0.4mmol) and compd E (0.22g, 0.8mmol) be dissolved in 25mL containing sodium carbonate (0.24g, in cellosolvo 3.2mmol), stirring heating, back flow reaction 5 hours at 135 DEG C; Naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, there is solid to separate out, filter, collect crude product, crude product uses deionized water, methanol wash for several times successively, obtain the P6 of 0.11g purifying through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 12.4%, and reaction formula is as follows:

The Structural Identification result of compound P6 is as follows:

Mass spectrum (MS m/z): 1104.2 (M+)

Ultimate analysis: C ₄₅h ₃₇f ₁₀irN ₈o ₂

Theoretical value: C, 48.96; H, 3.38; F, 17.21; Ir, 17.41; N, 10.15; O, 2.90

Measured value: C, 48.91; H, 3.44; F, 17.16; Ir, 17.44; N, 10.18; O, 2.87

The product P 6 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-4-hexyloxy pyrimidine-N, C ^2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close complex of iridium.

At 298K temperature, P6 (~ 10 ^-6m) CH ₂cl ₂in solution, the maximum emission peak of emmission spectrum is at 476nm place, has an acromion at 501nm place simultaneously; In addition, 10 ^-6the CH of M product P 6 ₂cl ₂solution at 298K temperature, with the CH of the FIrpic under the same terms ₂cl ₂solution is standard (Φ _pL=0.26) Φ of P6, is recorded _pL=0.05.

Embodiment 7

Present embodiments provide a kind of two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-eicosane oxygen yl pyrimidines-N, C ^2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close complex of iridium, its chemical structure is as shown in P8:

The preparation process of above-mentioned P8 is as follows:

S10, Compound C 8(2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-eicosane oxygen yl pyrimidines) synthesis

The compound A-28 (2-bromo-5-eicosane oxygen yl pyrimidines) providing following structural formula to represent and compd B (the fluoro-4-cyanophenylboronic acid of 3,5-bis-):

Under nitrogen protection, by compound A-28 (2.28g, 5mmol), compd B (1.37g, 7.5mmol) and Pd (PPh ₃) ₄(0.23mg, 0.2mmol) is dissolved in the DMF of 35mL, then adds the aqueous solution of 15mL containing sodium carbonate (1.59g, 15mmol), stirs 8 hours at 90 DEG C; After question response liquid cooling to room temperature, with dichloromethane extraction, separatory, then neutrality is washed to, filter with after anhydrous magnesium sulfate drying again, filtrate obtains crude product through removing desolventizing under reduced pressure, and to be the ethyl acetate of 1:5 again by volume ratio with the mixed solution of normal hexane be crude product that eluent carries out silica gel column chromatography is separated, and obtains 0.46g Compound C 8 after drying, yield 17.9%, reaction formula is as follows:

The Structural Identification result of Compound C 8 is as follows:

Mass spectrum (MS m/z): 513.3 (M+)

Ultimate analysis: C ₃₁h ₄₅f ₂n ₃o

Theoretical value: C, 72.48; H, 8.83; F, 7.40; N, 8.18; O, 3.11

Measured value: C, 72.43; H, 8.89; F, 7.34; N, 8.26; O, 3.08

The C8 that the above-mentioned reaction of above data acknowledgement obtains is 2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-eicosane oxygen yl pyrimidines;

S20, Compound D 8(part be 2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-eicosane oxygen yl pyrimidines containing iridium dichloro dimer) synthesis

Compound C 8 (1.03g, 2mmol) and three hydrated iridium trichloride (0.18g, 0.5mmol) being dissolved in 10mL volume ratio is, in the cellosolvo of 3:1 and the mixed solvent of water, be heated to reflux state stirring reaction 24 hours; After being chilled to room temperature, rotating and steam except partial solvent, then add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, and obtain the Compound D 8 of 0.08g after drying, yield is 12.8%, and reaction formula is as follows:

S30, P8(two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-eicosane oxygen yl pyrimidines-N, C ^2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close complex of iridium) synthesis

Compd E as described in Example 1 is provided;

Under nitrogen protection, Compound D 8 (0.75g, 0.3mmol) and compd E (0.25g, 0.9mmol) are dissolved in 30mL containing salt of wormwood (0.5g, in 2-methyl cellosolve 3.6mmol), be heated with stirring to 100 DEG C of back flow reaction 6 hours; Naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, there is solid to separate out, filter, collect crude product, crude product uses deionized water, methanol wash for several times successively, obtain the P8 of 0.03g purifying through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 3.3%, and reaction formula is as follows:

The Structural Identification result of compound P8 is as follows:

Structural Identification:

Mass spectrum (MS m/z): 1496.7 (M+)

Ultimate analysis: C ₇₃h ₉₃f ₁₀irN ₈o ₂

Theoretical value: C, 72.48; H, 8.83; F, 7.40; N, 8.18; O, 3.11

Measured value: C, 72.43; H, 8.89; F, 7.34; N, 8.26; O, 3.08

The product P 8 that the above-mentioned reaction of above data acknowledgement obtains is two (2-(3 ', 5 '-two fluoro-4 '-cyano-phenyl)-5-eicosane oxygen yl pyrimidines-N, C ^2') (2,4-bis-(trifluoromethyl)-5-(pyridine-2 '-Ji) pyrroles) close complex of iridium.

At 298K temperature, P8 (~ 10 ^-6m) CH ₂cl ₂in solution, the maximum emission peak of emmission spectrum is at 490nm place, has an acromion at 517nm place simultaneously; In addition, 10 ^-6the CH of M product P 8 ₂cl ₂solution at 298K temperature, with the CH of the FIrpic under the same terms ₂cl ₂solution is standard (Φ _pL=0.26) Φ of P8, is recorded _pL=0.005.

Embodiment 8

The doping object that the title complex P1 that the present embodiment provides with the embodiment of the present invention 1 is luminescent layer, prepare 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, electron injection buffer layer 308, the negative electrode 309 that stack gradually.

The preparation technology of this organic electroluminescence device comprises:

It is 100nm that a glass-based plate deposits a layer thickness, square resistance is that the tin indium oxide (ITO) of 10 ~ 20 Ω/mouth is as transparent anode 301, on anode 301, prepare that a layer thickness is 40nm successively by vacuum evaporation 4, 4', 4''-tri-(N-3-methylphenyl-N-phenyl is 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'-diphenylbenzidine (NPB) is as hole transmission layer 303, a layer thickness is 1 of 10nm, 3-two (9-carbazyl) benzene (mCP) is as electronic barrier layer 304, be that the mCP mixing material doped with 7wt%P1 of 30nm is as luminescent layer 305 with a layer thickness, on this luminescent layer 305, vacuum evaporation a layer thickness is successively 2 of 10nm again, 9-dimethyl-4, 7-phenylbenzene-phenanthrolene (BCP) is as hole blocking layer 306, thickness is three (oxine) aluminium (Alq of 35nm ₃) be that the lithium fluoride (LiF) of 1nm is as electron injection buffer layer 308 as electron transfer layer 307, thickness, the last vacuum plating of employing on the buffer layer techniques of deposition thickness is the metallic aluminium (Al) of 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 obtains, and slash "/" represents laminate structure.

Current versus brightness-the voltage characteristic of above-mentioned organic electroluminescence device is tested by Keithley source measuring system (Keithley2400Sourcemeter), with French its electroluminescent spectrum of JY company SPEX CCD3000 spectrometer measurement, all measurements all complete in atmosphere at room temperature, the maximum external quantum efficiency recording organic electroluminescence device is 8.0%, and maximum current efficiency is 9.2cd/A.

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, C ₁~ C ₂₀alkyl or 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 providing following structural formula to represent and compd B:

In formula, R is hydrogen atom, C ₁~ C ₂₀alkyl or C ₁~ C ₂₀alkoxyl group;

Under S20, protection of inert gas; described compd A and compd B are dissolved in the first organic solvent containing 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 6 ~ 12 hours at 80 ~ 100 DEG C; separation and purification reaction solution; obtain Compound C, its structural formula as shown at c:

In formula, R is hydrogen atom, C ₁~ C ₂₀alkyl or 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 hydrated iridium trichloride are dissolved in volume ratio by the mol ratio of 2:1 ~ 4:1; be heated to reflux state stirring reaction subsequently after 24 hours; be cooled to room temperature; separation and purification; obtain Compound D, its structural formula as shown atd:

In formula, R is hydrogen atom, C ₁~ C ₂₀alkyl or C ₁~ C ₂₀alkoxyl group;

S40, the compd E providing following structural formula to represent:

E：

Under protection of inert gas; described Compound D and compd E are dissolved in the second organic solvent containing sodium carbonate or salt of wormwood by the mol ratio of 1:2 ~ 1:3; obtain mixing solutions; described mixing solutions carried out Suzuki linked reaction after 5 ~ 10 hours at 84 ~ 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, C ₁~ C ₂₀alkyl or C ₁~ C ₂₀alkoxyl group.

3. the preparation method of blue-ray organic electroluminescent material as claimed in claim 2, it is characterized in that, in described S20, the concentration of described compd A in reaction solution is 0.1 ~ 0.2mol/L; Described 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) changes palladium or four (triphenylphosphines) close palladium, and the mole dosage of described palladium catalyst is 2% ~ 5% times of compd A; Described alkali is wet chemical or aqueous sodium carbonate, and the mole dosage of described alkali is 1 ~ 3 times of compd A.

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: after reaction solution is cooled to room temperature, adopt dichloromethane extraction, then neutrality is washed with water to, again after anhydrous magnesium sulfate drying, filtration obtains filtrate, gained filtrate obtains crude product after removing desolventizing under reduced pressure, to be ethyl acetate and the normal hexane mixed solution of 1:5 ~ 1:10 be crude product volume ratio that eluent carries out silica gel column chromatography is separated, and obtains 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: after question response stops being chilled to room temperature, rotate and steam except partial solvent, add appropriate distilled water, filter and obtain solid, solid uses distilled water, methanol wash successively, obtains described Compound D after drying.

7. the preparation method of blue-ray organic electroluminescent material as claimed in claim 2, it is characterized in that, in described S40, described second organic solvent is 2-methyl cellosolve or cellosolvo.

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, and the mole dosage of described sodium methylate or sodium ethylate is 8 ~ 12 times of Compound D.

9. the preparation method of blue-ray organic electroluminescent material as claimed in claim 2, it is characterized in that, in described S40, described purification procedures comprises: after question response stops being chilled to room temperature, and concentrated remove portion solvent, adds appropriate distilled water, have solid to separate out; Collecting by filtration crude product, after crude product uses 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, doped with the such as blue-ray organic electroluminescent material shown in structural formula P in described luminescent layer:

In formula, R is hydrogen atom, C ₁~ C ₂₀alkyl or C ₁~ C ₂₀alkoxyl group.