CN103172676A - Iridium-containing organic electroluminescence material, preparation method and organic electroluminescent device - Google Patents
Iridium-containing organic electroluminescence material, preparation method and organic electroluminescent device Download PDFInfo
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- CN103172676A CN103172676A CN201110430597XA CN201110430597A CN103172676A CN 103172676 A CN103172676 A CN 103172676A CN 201110430597X A CN201110430597X A CN 201110430597XA CN 201110430597 A CN201110430597 A CN 201110430597A CN 103172676 A CN103172676 A CN 103172676A
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- 0 C**c(ccc(F)n1)c1F Chemical compound C**c(ccc(F)n1)c1F 0.000 description 2
- KQPADHIQGMVMOF-UHFFFAOYSA-N COc1ccnc(-c(ccc(F)n2)c2F)c1 Chemical compound COc1ccnc(-c(ccc(F)n2)c2F)c1 KQPADHIQGMVMOF-UHFFFAOYSA-N 0.000 description 1
- MBTGBRYMJKYYOE-UHFFFAOYSA-N Fc1cccc(F)n1 Chemical compound Fc1cccc(F)n1 MBTGBRYMJKYYOE-UHFFFAOYSA-N 0.000 description 1
- PVMLJDLTWMGZAH-UHFFFAOYSA-N c1n[nH]c(-c2ncccc2)n1 Chemical compound c1n[nH]c(-c2ncccc2)n1 PVMLJDLTWMGZAH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the photoelectric material field, and discloses an iridium-containing organic electroluminescence material, a preparation method and an organic electroluminescent device; the iridium-containing organic electroluminescence material comprises a following structural formula: in the formula, R is C1-C4 alkyl. A molecular structure of the iridium-containing organic electroluminescence material contains a dipyridine ligand, an alkoxyl group and a fluorine group; so that the carrier injection and transmission capability of the polymer can be enhanced, and the iridium-containing organic electroluminescence material has high internal quantum efficiency and electroluminescent efficiency; in addition, the iridium-containing organic electroluminescence material employs a strong field ligand 2-picolinic acid as an auxiliary ligand, thereby the luminescence spectrum enables effective blue shift, and the luminescence efficiency of blue light phosphorescence can be greatly enhanced.
Description
Technical field
The present invention relates to field of photovoltaic materials, relate in particular to a kind of containing iridium organic electroluminescent compounds and preparation method thereof.The invention still further relates to a kind of luminescent layer and include this organic electroluminescence device containing the polymerization of iridium organic electroluminescent.
Background technology
Organic electroluminescent (EL) refers to that organic materials is under electric field action, electric energy is converted into to a kind of luminescence phenomenon of luminous energy.In early days former because the driving voltage of made device is too high, luminous efficiency is low etc. thereby make the research to organic electroluminescent stay cool.Until 1987, the people such as the Tang of Kodak have invented with oxine aluminium (Alq in document and patent US4356429
3) be luminescent material, make the high-quality thin film of even compact with aromatic diamine, made low-work voltage, high brightness, high efficiency organic electroluminescence device, opened the new prelude to electroluminescent organic material research.But, due to the restriction of the statistical theory that is subject to spinning, the theoretical internal quantum efficiency limit of fluorescent material is only 25%, how takes full advantage of all the other phosphorescence of 75% and realize that higher luminous efficiency has become the hot research direction in this field after this.1997, Forrest etc. found the electrophosphorescence phenomenon, and the internal quantum efficiency of electroluminescent organic material is broken through 25% restriction, makes the research of electroluminescent organic material enter another new period.
In research subsequently, the title complex of small molecules doping type transition metal has become people's research emphasis, as the title complex of iridium, ruthenium, platinum etc.The advantage of this class title complex is that they can obtain very high emitted energy from the triplet state of self, and metal iridium (III) compound wherein, good stability due to its compound, reaction conditions gentleness in building-up process, and there is very high electroluminescent properties, accounting for dominant position always in research process subsequently.And, in order to make device obtain full-color demonstration, generally must obtain ruddiness, green glow and the blue light material of excellent performance simultaneously.With ruddiness, with green light material, compare, the development of blue light material lags behind comparatively speaking, and the efficiency that improves blue light material has just become the breakthrough point of people's researchs with purity of color.Up to now, two [2-(2,4 difluorobenzene base) pyridine-N, C
2] (pyridine carboxylic acid) to close iridium (FIrpic) be that the document patent report obtains one of Ir (III) a metal-organic complex blue phosphorescent electroluminescent material at most.Although people have carried out various optimization to FIrpic class OLED structure, device performance also is greatly improved, but the weakness of FIrpic maximum is exactly sent out blue light is sky blue, blue light color purity is not good enough, the CIE of each OLED device of making changes between (0.13～0.17,0.29～0.39).Therefore, develop highly purified blue phosphorescent organic electroluminescent material and become a megatrend of expanding the blue light material research field.
Summary of the invention
The object of the present invention is to provide a kind of can send blue emitting phosphor containing the iridium organic electroluminescent compounds.
Provided by the invention containing the iridium organic electroluminescent compounds, there is following general structural formula:
In formula, R is C
1～C
4alkyl.
Another object of the present invention is to provide the above-mentioned preparation method containing the iridium organic electroluminescent compounds, its step is as follows:
In S1, oxygen-free environment, by general structure, be
compd A and three hydration iridous chlorides according to mol ratio, within 3: 1～5: 1, add in the first organic solvent (as, cellosolvo), after dissolving, be warming up to the first organic solvent reflux state, reaction generating structure formula is
two endo compound B; Wherein, R is C
1～C
4alkyl;
In S2, oxygen-free environment, by described two endo compound B and structural formula, be
5-(2 '-pyridyl)-1,2, the 4-triazole according to mol ratio within 1: 2.5～1: 3.5, add the second organic solvent (as, 1,2-ethylene dichloride, trichloromethane, cellosolvo or tetrahydrofuran (THF)) in, then toward add in the second organic solvent the first catalyzer (as, sodium methylate and silver triflate co-catalyst, and the mol ratio of sodium methylate and silver triflate is 5: 1), stir and be warming up to the second organic solvent reflux state, the generating structure general formula is
described containing the iridium organic electroluminescent compounds.
In the above-mentioned preparation method's containing the iridium organic electroluminescent compounds step S1, described compd A is to adopt following step to make:
S11, in the anhydrous and oxygen-free environment, by structural formula, be
compound D and diisopropylamine lithium according to mol ratio, add at 1.2: 1 in tetrahydrofuran (THF) (THF) solution, under-78 ℃, reacted; Then toward reaction mixture, add trimethyl borate, continue reaction at normal temperatures, the generating structure formula as
compd E;
S12, by described compd E and general structure, be
compound F 17-hydroxy-corticosterone within 1.5: 1～2: 1, add and contain catalyzer (as, K according to mol ratio
2cO
3the aqueous solution and Pd (PPh
3)
4mixture, described K
2cO
310 times of the molar weight molar weight that is described compound F 17-hydroxy-corticosterone, described Pd (PPh
3)
4the molar weight molar weight that is described compound F 17-hydroxy-corticosterone 0.5%) the 3rd organic solvent (as, tetrahydrofuran (THF), dioxane, toluene or dimethyl sulfoxide (DMSO)), be warming up under the 3rd organic solvent reflux state and carry out the Suzuki linked reaction, generate described compd A; Wherein, in described compound F 17-hydroxy-corticosterone, R is C
1～C
4alkyl.
Wherein, also comprise the purification step to compd E in described step S11:
The NaOH aqueous solution that is 5wt% with the quality percentage composition to react in the termination reaction mixed solution; The pH value of the HCl aqueous solution conditioned reaction mixed solution that is then 3N by equivalent concentration is to neutral; Then by ethyl acetate, repeatedly extract rear merging organic phase; Finally concentrate organic phase, obtain the described compd E of purifying.
Wherein, also comprise the step that compd A is purified in described step S12:
Toward containing after adding appropriate distilled water in the reaction mixture of described compd A, then by ethyl acetate, repeatedly extract, merge organic phase; Secondly use anhydrous MgSO
4dry organic phase, filter concentrated filtrate; Finally use ethyl acetate and normal hexane mixed solution to make eluent and the filtrate residue is carried out to silica gel column chromatography separate, obtain the described compd A of purifying.
Another goal of the invention of the present invention is to provide a kind of organic electroluminescence device, and the luminescent layer of this organic electroluminescence device comprises containing the iridium organic electroluminescent compounds having following structural formula containing the iridium organic electroluminescent compounds:
In formula, R is C
1～C
4alkyl.
The iridium organic electroluminescent compounds that contains provided by the invention, contain bipyridine ligand in its molecular structure, and also with alkoxyl group and fluorine-based; Like this, just improved carrier injection and the transmittability of this polymkeric substance, made it there is higher internal quantum efficiency and electroluminescent efficiency; In addition, adopting high field part 2-pyridine carboxylic acid containing the iridium organic electroluminescent compounds is assistant ligand, makes the effective blue shift of its luminescent spectrum, has greatly increased the luminous efficiency of blue emitting phosphor.
The accompanying drawing explanation
Fig. 1 is containing iridium organic electroluminescent compounds (dfpymopy) in embodiment 1
2the CH of Ir (PZ)
2cl
2the PL spectrogram of solution under 298K;
The structural representation that Fig. 2 is organic electroluminescence device in embodiment 5.
Embodiment
Provided by the invention containing the iridium organic electroluminescent compounds, iridium (Ir) a metal-organic complex is a kind of phosphorescent light-emitting materials with shorter phosphorescent lifetime (1～14 μ s); Containing the iridium organic electroluminescent compounds, there is molecular formula (dfpyORpy)
2irpic; Wherein, dfpy represents on cyclic metal complexes one 2, two fluorine-based substituent pyridine rings of 6-bit strip; ORpy represents the pyridine ring of another 4-bit strip alkoxy substituent on cyclic metal complexes; Two pyridine rings connect into dipyridyl with 2-, 3-position respectively; Pic means assistant ligand pyridine carboxylic acid in title complex.Described containing the iridium organic electroluminescent compounds, there is following structural formula:
In formula, " 2 " mean that this general structure contains two structures and is
ligand; After the said structure formula is launched, its representation is as follows:
Wherein, R is C
1～C
4alkyl.
The iridium organic electroluminescent compounds that contains provided by the invention, contain bipyridine ligand in its molecular structure, and also with alkoxyl group and fluorine-based; Like this, just improved carrier injection and the transmittability of this polymkeric substance, made it there is higher internal quantum efficiency and electroluminescent efficiency; In addition, adopting high field part 2-pyridine carboxylic acid containing the iridium organic electroluminescent compounds is assistant ligand, makes the effective blue shift of its luminescent spectrum, has greatly increased the luminous efficiency of blue emitting phosphor.
The above-mentioned preparation method containing the iridium organic electroluminescent compounds, its step is as follows:
In S1, oxygen-free environment (being formed by rare gas element, as nitrogen atmosphere or argon gas atmosphere), by structural formula, be
compd A and three hydration iridous chloride (lrCl
33H
2o) according to mol ratio 3: 1～5: 1 (preferably 4: 1) add the first organic solvent (as, cellosolvo) in, after dissolving, be warming up to 135 ℃ (, the boiling temperature of cellosolvo, the reflux temperature of cellosolvo namely) back flow reaction, the generating structure general formula is
two endo compound B ((dfpyORpy)
2ir (μ-Cl)-(dfpyORpy)
2); Wherein, R is C
1～C
4alkyl; This reaction formula is as follows:
In S2, oxygen-free environment (being formed by rare gas element, as nitrogen atmosphere or argon gas atmosphere), by described two endo compound B and structural formula, be
5-(2 '-pyridyl)-1,2, the 4-triazole according to mol ratio 1: 2.5～1: 3.5 (preferably 1: 3) add the second organic solvent (as, 1,2-ethylene dichloride, trichloromethane, cellosolvo or tetrahydrofuran (THF) (THF)) in, the co-catalyst effect that the sodium methylate that is 5: 1 in mol ratio and silver triflate (AgOTf) form, be warming up to 61 ℃～135 ℃ (the boiling temperature scopes that this temperature range is the second organic solvent, the reflux temperature of the second organic solvent namely) carry out ligand exchange reaction, the generating structure formula under reflux state
for containing iridium organic electroluminescent compounds, i.e. (dfpyORpy)
2ir (PZ); Wherein, the second different organic solvents, its reflux temperature difference, as, 1,2-ethylene dichloride, trichloromethane, cellosolvo and the tetrahydrofuran (THF) reflux temperature of correspondence respectively are 83.5 ℃, 61.5 ℃, 135 ℃ and 63.5 ℃; This reaction formula is as follows:
Above-mentioned containing in iridium organic electroluminescent compounds preparation method's step S1, described compd A is to adopt following step to make:
S11, in anhydrous and oxygen-free environment (being formed by rare gas element, as nitrogen atmosphere or argon gas atmosphere), by structural formula, be
compound D (2, the 6-difluoro pyridine) and diisopropylamine lithium (be called for short LDA) according to mol ratio, add at 1.2: 1 in tetrahydrofuran (THF) (THF) solution, under-78 ℃, reacted, the reaction times is probably 0.5～2h, make 2,6-difluoro pyridine base-3-lithium; Then toward reaction mixture, add the trimethyl borate (B (OMe) of 12.5mmol
3), 2,6-difluoro pyridine base-3-lithium and trimethyl borate (B (OMe)
3) continue reaction at normal temperatures, the generating structure formula as
compd E (2, the fluoro-3-boric acid of 6-bis-pyridine); Reaction formula is as follows:
S12, by described compd E and general structure, be
compound F 17-hydroxy-corticosterone (4-alkyl-2-bromopyridine) add and contain catalyzer (as, K according to mol ratio 1.5: 1～2: 1 (preferably 1.6: 1)
2cO
3the aqueous solution and Pd (PPh
3)
4mixture, described K
2cO
310 times of the molar weight molar weight that is described compound F 17-hydroxy-corticosterone, described Pd (PPh
3)
4the molar weight molar weight that is described compound F 17-hydroxy-corticosterone 0.5%) the 3rd organic solvent (as, tetrahydrofuran (THF), dioxane, toluene or dimethyl sulfoxide (DMSO) etc.), be warming up to 70～100 ℃ of (reflow temperature range of the 3rd organic solvent namely; Because each self-corresponding boiling temperature of tetrahydrofuran (THF), dioxane, toluene or dimethyl sulfoxide (DMSO) is respectively 63.5 ℃, 101.5 ℃, 110.8 ℃ and 189 ℃, when these the 3rd organic solvents, with after water mixes, its reflux temperature can change to some extent; Boiling temperature is during lower than the boiling temperature of water, and its reflux temperature is probably 70 ℃, when the boiling point of solvent temperature during higher than water pretty young woman boiling temperature, the boiling temperature that reflux temperature is water, 100 ℃) under reflux state, carry out the Suzuki linked reaction, generate described compd A; Wherein, in compound F 17-hydroxy-corticosterone, R is C
1～C
4alkyl; Reaction formula is as follows:
Wherein, also comprise the step that compd E is purified in described step S11:
The NaOH aqueous solution that is 5wt% with the quality percentage composition to react in the termination reaction mixed solution; The pH value of the HCl aqueous solution conditioned reaction mixed solution that is then 3N by equivalent concentration is to neutral; Then by ethyl acetate, repeatedly extract rear merging organic phase; Finally concentrate organic phase, obtain the described compd E of purifying.
Wherein, also comprise the step that compd A is purified in described step S12:
Toward containing after adding appropriate distilled water in the reaction mixture of described compd A, then by ethyl acetate, repeatedly extract, merge organic phase; Secondly use anhydrous MgSO
4dry organic phase, filter concentrated filtrate; The mixed solution that finally uses ethyl acetate to be mixed to form with normal hexane is made eluent and the filtrate residue is carried out to silica gel column chromatography is separated, and obtains the described compd A of purifying.
Above-mentioned, containing in the preparation method of iridium organic electroluminescent compounds, in order to obtain more highly purified compd B, need the compd B that step S1 is made to carry out purification processes, its treating processes is as follows:
S11, reaction mixture is carried out to the concentrating under reduced pressure processing;
S12, take methylene dichloride as elutriant carries out the silica gel column chromatography separation to concentrated solution, obtain the compd B of purifying.
In like manner, containing in the preparation method of iridium organic electroluminescent compounds, more highly purified containing the iridium organic electroluminescent compounds in order to obtain above-mentioned, need the iridium organic electroluminescent compounds that contains that step S2 is made to carry out purification processes, its treating processes is as follows:
S21, the suitable concentrated reaction mixture containing the iridium organic electroluminescent compounds, after removing a part of solvent, the appropriate distilled water of impouring is to separate out solid;
Crude product is collected in S22, filtration, uses successively normal hexane, ether supersound washing;
S23, the normal hexane of take separate as elutriant carries out silica gel column chromatography to it with the mixed solution of methylene dichloride, obtain purifying containing the iridium organic electroluminescent compounds.
Have consistency preferably containing the material of main part in iridium organic electroluminescent compounds and organic electroluminescence device luminescent layer, the doping object can be used as in luminescent layer is widely used in the organic electroluminescence device for preparing blue or white phosphorescence; Should there is following general structure containing the iridium organic electroluminescent compounds:
In formula, R is C
1～C
4alkyl.
The iridium organic electroluminescent compounds that contains provided by the invention, contain bipyridine ligand in its molecular structure, and also with alkoxyl group and fluorine-based; Like this, just improved carrier injection and the transmittability of this polymkeric substance, made it there is higher internal quantum efficiency and electroluminescent efficiency; In addition, adopting high field part 2-pyridine carboxylic acid containing the iridium organic electroluminescent compounds is assistant ligand, makes the effective blue shift of its luminescent spectrum, has greatly increased the luminous efficiency of blue emitting phosphor.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
The present embodiment containing the iridium organic electroluminescent compounds, title complex two (2 ', 6 '-bis-fluoro-4-methoxyl groups-2,3 '-dipyridyl-N, C
2') (5-(2 '-pyridyl)-1,2, the 4-triazole) tetrazolium) close iridium [(dfpymopy)
2ir (PZ)], wherein R is methyl:
Title complex two (2 ', 6 '-bis-fluoro-4-methoxyl groups-2,3 '-dipyridyl-N, C
2') (5-(2 '-pyridyl)-1,2,4-triazole) tetrazolium) and close iridium preparation technology as follows:
Synthesizing of the fluoro-3-boric acid of (1) 2,6-bis-pyridine
Under nitrogen protection, the N-Lithiodiisopropylamide of 7.5mL (12mmol) 1.6M and 0.91mL (10mmol) 2, the 6-difluoro pyridine adds in the 40mL tetrahydrofuran solution, keeps-78 ℃ of temperature stirring reaction 1h.The question response system is warming up to room temperature after adding 1.40mL (12.5mmol) trimethyl borate naturally, continues stirring reaction 1h.Reaction mixture slowly adds the NaOH aqueous solution termination reaction that 20mL quality percentage composition is 5wt%, after stirring 10min, dropwise adds the HCl aqueous solution adjust pH that appropriate equivalent concentration is 3N extremely neutral.Ethyl acetate repeatedly extracts, and merges organic phase, and rotation is steamed and desolventized, and obtains white solid thing 1.43g, and yield is 90%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.45(d，1H)，6.94(d，1H)，5.33(s，2H).
(2) 2 ', 6 '-bis-fluoro-4-methoxyl groups-2,3 '-dipyridyl [dfpymopy] synthetic
Under nitrogen protection, the bromo-4-methoxypyridine of 0.75g (4.00mmol) 2-, 1.02g (6.40mmol) 2, the fluoro-3-boric acid of 6-bis-pyridine, 0.0374g (0.032mmol) Pd (PPh
3)
4after being dissolved in 25mL THF, add the K that 10mL quality percentage composition is 5wt%
2cO
3the aqueous solution, be heated to 70 ℃ of reflux states, stirring reaction 18h.Naturally after being chilled to room temperature, add appropriate distilled water, appropriate ethyl acetate repeatedly extracts.Merge organic phase, anhydrous MgSO
4dry.Filter, filtrate decompression obtains crude product after steaming and desolventizing.Take ethyl acetate: normal hexane (v/v)=1: 5, as elutriant carries out the silica gel column chromatography separation, obtains colorless solid product 0.54g, and yield is 60.7%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.91(d，1H)，8.63(d，1H)，7.75(d，1H)，7.43(d，1H)，6.86(s，1H)，3.85(s，3H).
(3) two endo compounds (dfpymopy)
2ir (μ-Cl) Ir (dfpymopy)
2synthetic
Under nitrogen protection, 1.78g (8mmol) 2 ', 6 '-bis-fluoro-4-methoxyl groups-2,3 '-dipyridyl and 0.71g (2mmol) three hydration iridous chlorides are dissolved in the 30mL cellosolvo, are heated to 135 ℃ of reflux states, stirring reaction 25h.Naturally after being chilled to room temperature, concentrating under reduced pressure; Take methylene dichloride as the elutriant silica gel column chromatography separates, obtain product 0.94g, yield is 70.1%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.82(d，4H)，7.66(d，4H)，7.35(d，4H)，6.74(s，4H)，3.89(s，12H).
(4) title complex two (2 ', 6 '-bis-fluoro-4-methoxyl groups-2,3 '-dipyridyl-N, C
2') (5-(2 '-pyridyl)-1,2, the 4-triazole) tetrazolium) close iridium [(dfpymopy)
2ir (PZ)] synthetic
Under nitrogen protection, 0.44g (3mmol) 5-(2 '-pyridyl)-1,2,4-triazole and 1.34g (1mmol) two endo compounds (dfpymopy)
2ir (μ-Cl) Ir (dfpymopy)
2be dissolved in the 60mL trichloromethane, under the katalysis of 0.54g (10mmol) sodium methylate and 0.44g (2mmol) silver triflate, stirring heating is warming up to 61.5 ℃ of reflux states, reaction 24h.Naturally after being chilled to room temperature, concentrating and remove a part of solvent, the appropriate distilled water of impouring, have solid to separate out.Filter, collect crude product, solid is successively with after deionized water, ether washing for several times, take ethyl acetate: normal hexane=1: 3 (volume ratio), as elutriant carries out the silica gel column chromatography separation to it, obtains 0.85g, pure products (dfpymopy)
2ir (PZ), yield is 54.5%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.80(d，1H)，8.78(d，1H)，8.56(d，1H)，8.22(s，1H)，7.93(d，1H)，7.76(t，1H)，7.60(d，1H)，7.58(d，1H)，7.28(m，1H)，7.22(s，1H)，7.17(s，1H)，6.66(s，1H)，6.61(s，1H)，3.85(s，6H)
Fig. 1 is containing iridium organic electroluminescent compounds (dfpymopy) in embodiment 1
2the CH of Ir (PZ)
2cl
2the PL spectrogram of solution under 298K; Wherein, test condition is: under 298K, volumetric molar concentration is～10
-5the CH of M
2cl
2solution, with the H of 0.1N sulfuric acid Kui Lin
2sO4 solution is standard, the Φ of standardized solution
pL=0.54 carries out; As shown in Figure 1, λ
max pLduring=440nm, at the 460nm place, one acromion is arranged.
Embodiment 2
The present embodiment containing the iridium organic electroluminescent compounds, title complex two (2 ', 6 '-bis-fluoro-4-oxyethyl groups-2,3 '-dipyridyl-N, C
2') (5-(2 '-than pyridine base)-1,2, the 4-triazole) close iridium, wherein R is ethyl:
Title complex two (2 ', 6 '-bis-fluoro-4-oxyethyl groups-2,3 '-dipyridyl-N, C
2') (5-(2 '-pyridyl)-1,2,4-triazole) to close the preparation technology of iridium as follows:
Synthesizing of the fluoro-3-boric acid of (1) 2,6-bis-pyridine is identical with the step (1) in case study on implementation 1;
(2) 2 ', 6 '-bis-fluoro-4-oxyethyl groups-2,3 '-dipyridyl synthetic
Under argon shield, the bromo-4-ethoxy pyridine of (0.81g, 4.00mmol) 2-, (1.02g, 6.40mmol) 2, the fluoro-3-boric acid of 6-bis-pyridine, 0.0374g (0.032mmol) Pd (PPh
3)
44after being dissolved in the 30mL dioxane, add the K that 10mL quality percentage composition is 5wt%
2cO
3the aqueous solution, be heated to 100 ℃ of reflux states, stirring reaction 18h.Naturally after being chilled to room temperature, add appropriate distilled water, appropriate ethyl acetate repeatedly extracts.Merge organic phase, anhydrous MgSO
4dry.Obtain crude product after removing solvent under reduced pressure.Take ethyl acetate: normal hexane (v/v)=1: 4, as elutriant carries out the silica gel column chromatography separation, obtains colorless solid product 0.56g, and yield is 59.6%.
1H?MR(400MHz，CDCl
3，ppm)：δ8.92(d，1H)，8.65(d，1H)，7.75(d，1H)，7.43(d，1H)，6.92(s，1H)，4.12(m，2H)，1.90(m，3H).
Synthesizing of (3) two endo compounds
Under argon shield, 1.89g (8mmol) 2 ', 6 '-bis-fluoro-4-oxyethyl groups-2,3 '-dipyridyl and 0.71g (2mmol) three hydration iridous chlorides are dissolved in the 30mL cellosolvo, are heated to 135 ℃ of reflux states, stirring reaction 24h.Naturally after being chilled to room temperature, concentrating under reduced pressure; Take methylene dichloride as the elutriant silica gel column chromatography separates, obtain product 0.99g, yield is 70.9%.
1H?MR(400MHz，CDCl
3，ppm)：δ8.83(d，4H)，7.66(d，4H)，7.35(d，4H)，6.74(s，4H)，4.11(m，8H)，1.88(m，12H).
(4) title complex two (2 ', 6 '-bis-fluoro-4-oxyethyl groups-2,3 '-dipyridyl-N, C
2') (5-(2 '-pyridyl)-1,2, the 4-triazole) close synthesizing of iridium
Under the protection of argon gas gas; 0.37g (2.5mmol) 5-(2 '-pyridyl)-1; 2; 4-triazole and 1.40g (1mmol) two endo compounds are dissolved in 60mL1; in the 2-ethylene dichloride; under the katalysis of 0.54g (10mmol) sodium methylate and 0.44g (2mmol) silver triflate, stirring heating is warming up to 83.5 ℃ of reflux states, reaction 24h.Naturally after being chilled to room temperature, concentrating and remove a part of solvent, the appropriate distilled water of impouring, have solid to separate out.Filter, collect crude product, solid is successively with after deionized water, ether washing for several times, take ethyl acetate: normal hexane=1: 3 (volume ratio), as elutriant carries out the silica gel column chromatography separation to it, obtains the 0.71g pure products, and yield is 43.9%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.80(d，1H)，8.78(d，1H)，8.57(d，1H)，8.22(s，1H)，7.94(d，1H)，7.76(t，1H)，7.60(d，1H)，7.55(d，1H)，7.28(m，1H)，7.22(s，1H)，7.18(s，1H)，6.68(s，1H)，6.63(s，1H)，4.08(m，4H)，1.82(m，6H).
Embodiment 3
The present embodiment containing the iridium organic electroluminescent compounds, title complex two (2 ', 6 '-bis-fluoro-4-propoxy--2,3 '-dipyridyl-N, C
2') (5-(2 '-pyridyl)-1,2, the 4-triazole) close iridium, wherein R is propyl group:
Title complex two (2 ', 6 '-bis-fluoro-4-propoxy--2,3 '-dipyridyl-N, C
2') (5-(2 '-pyridyl)-1,2,4-triazole) to close the preparation technology of iridium as follows:
Synthesizing of the fluoro-3-boric acid of (1) 2,6-bis-pyridine is identical with the step (1) in case study on implementation 1;
(2) 2 ', 6 '-bis-fluoro-4-propoxy--2,3 '-dipyridyl synthetic
Under nitrogen protection, the bromo-4-propoxy-of (0.86g, 4.00mmol) 2-pyridine, (1.02g, 6.40mmol) 2, the fluoro-3-boric acid of 6-bis-pyridine, 0.0374g (0.032mmol) Pd (PPh
3)
44after being dissolved in 25mL dimethyl sulfoxide (DMSO) (DMSO), add the K that 10mL quality percentage composition is 5wt%
2cO
3the aqueous solution, 100 ℃ of heat temperature raisings are to reflux state, stirring reaction 18h.Naturally after being chilled to room temperature, add appropriate distilled water, appropriate ethyl acetate repeatedly extracts.Merge organic phase, anhydrous MgSO
4dry.Obtain crude product after removing solvent under reduced pressure.Take ethyl acetate: normal hexane (v/v)=1: 4, as elutriant carries out the silica gel column chromatography separation, obtains colorless solid product 0.57g, and yield is 57.0%.
1H?MR(400MHz，CDCl
3，ppm)：δ8.91(d，1H)，8.66(d，1H)，7.76(d，1H)，7.44(d，1H)，6.91(s，1H)，4.08(m，2H)，1.76(m，2H)，0.98(m，3H).
Synthesizing of (3) two endo compounds
Under nitrogen protection, 2.00g (8mmol) 2 ', 6 '-bis-fluoro-4-propoxy--2,3 '-dipyridyl and 0.71g (2mmol) three hydration iridous chlorides are dissolved in the 30mL cellosolvo, are heated to 135 ℃ of reflux states, stirring reaction 24h.Naturally after being chilled to room temperature, concentrating under reduced pressure; Take methylene dichloride as the elutriant silica gel column chromatography separates, obtain product 0.99g, yield is 68.2%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.80(d，4H)，7.64(d，4H)，7.34(d，4H)，6.71(s，4H)，4.10(m，8H)，1.87(m，8H)，0.98(m，12H).
(4) title complex two (2 ', 6 '-bis-fluoro-4-propoxy--2,3 '-dipyridyl-N, C
2') (5-(2 '-pyridyl)-1,2, the 4-triazole) close synthesizing of iridium
Under nitrogen protection; 0.51g (3.5mmol) 5-(2 '-pyridyl)-1; 2; 4-triazole and 1.45g (1mmol) two endo compounds are dissolved in the 60mL tetrahydrofuran (THF); under the katalysis of 0.54g (10mmol) sodium methylate and 0.44g (2mmol) silver triflate; stirring heating is warming up to 63.5 ℃ of reflux states, reaction 24h.Naturally after being chilled to room temperature, concentrating and remove a part of solvent, the appropriate distilled water of impouring, have solid to separate out.Filter, collect crude product, solid is successively with after deionized water, ether washing for several times, take ethyl acetate: normal hexane=1: 3 (volume ratio), as elutriant carries out the silica gel column chromatography separation to it, obtains the 0.77g pure products, and yield is 46.1%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.81(d，1H)，8.78(d，1H)，8.56(d，1H)，8.23(s，1H)，7.93(d，1H)，7.78(t，1H)，7.58(d，1H)，7.54(d，1H)，7.28(m，1H)，7.22(s，1H)，7.17(s，1H)，6.68(s，1H)，6.62(s，1H)，4.08(m，4H)，1.84(m，4H)，0.99(m，6H).
Embodiment 4:
The present embodiment containing the iridium organic electroluminescent compounds, title complex two (2 ', 6 '-bis-fluoro-4-butoxy-2,3 '-dipyridyl-N, C
2') (5-(2 '-pyridyl)-1,2, the 4-triazole) close iridium, wherein R is butyl:
Title complex two (2 ', 6 '-bis-fluoro-4-butoxy-2,3 '-dipyridyl-N, C
2') (5-(2 '-pyridyl)-1,2,4-triazole) to close the preparation technology of iridium as follows:
Synthesizing of the fluoro-3-boric acid of (1) 2,6-bis-pyridine is identical with the step (1) in case study on implementation 1;
(2) 2 ', 6 '-bis-fluoro-4-butoxy-2,3 '-dipyridyl synthetic
Under nitrogen protection, the bromo-4-butoxy of (0.92g, 4.00mmol) 2-pyridine, (1.02g, 6.40mmol) 2, the fluoro-3-boric acid of 6-bis-pyridine, 0.0374g (0.032mmol) Pd (PPh
3)
4after being dissolved in 25mL toluene, add the K that 10mL quality percentage composition is 5wt%
2cO
3the aqueous solution, be heated to 100 ℃ of reflux states, stirring reaction 18h.Naturally after being chilled to room temperature, add appropriate distilled water, appropriate ethyl acetate repeatedly extracts.Merge organic phase, anhydrous MgSO
4dry.Obtain crude product after removing solvent under reduced pressure.Take ethyl acetate: normal hexane (v/v)=1: 4, as elutriant carries out the silica gel column chromatography separation, obtains colorless solid product 0.59g, and yield is 55.7%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.93(d，1H)，8.67(d，1H)，7.75(d，1H)，7.45(d，1H)，6.95(s，1H)，4.07(m，2H)，1.75(m，2H)，1.54(m，2H)，0.89(m，3H).
Synthesizing of (3) two endo compounds
Under nitrogen protection, 2.11g (8mmol) 2 ', 6 '-bis-fluoro-4-butoxy-2,3 '-dipyridyl and 0.71g (2mmol) three hydration iridous chlorides are dissolved in the 30mL cellosolvo, are heated to 135 ℃ of reflux states, stirring reaction 24h.Naturally after being chilled to room temperature, concentrating under reduced pressure; Take methylene dichloride as the elutriant silica gel column chromatography separates, obtain product 1.00g, yield is 66.3%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.82(d，4H)，7.66(d，4H)，7.35(d，4H)，6.73(s，4H)，4.08(m，8H)，1.77(m，8H)，1.53(m，8H)，0.90(m，12H).
(4) title complex two (2 ', 6 '-bis-fluoro-4-butoxy-2,3 '-dipyridyl-N, C
2') (5-(2 '-pyridyl)-1,2, the 4-triazole) close synthesizing of iridium
Under nitrogen protection; 0.58g (3mmol) 5-(2 '-pyridyl)-1; 2; 4-triazole and 1.51g (1mmol) two endo compounds are dissolved in the 60mL2-ethoxy ethanol; under the katalysis of 0.54g (10mmol) sodium methylate and 0.44g (2mmol) silver triflate; stirring heating is warming up to 135 ℃ of reflux states, reaction 24h.Naturally after being chilled to room temperature, concentrating and remove a part of solvent, the appropriate distilled water of impouring, have solid to separate out.Filter, collect crude product, solid is successively with after deionized water, ether washing for several times, take ethyl acetate: normal hexane=1: 3 (volume ratio), as elutriant carries out the silica gel column chromatography separation to it, obtains the 0.83g pure products, and yield is 48.0%.
1H?NMR(400MHz，CDCl
3，ppm)：δ8.79(d，1H)，8.76(d，1H)，8.57(d，1H)，8.22(s，1H)，7.94(d，1H)，7.76(t，1H)，7.60(d，1H)，7.55(d，1H)，7.28(m，1H)，7.21(s，1H)，7.17(s，1H)，6.67(s，1H)，6.62(s，1H)，4.06(m，4H)，1.75(m，4H)，1.50(m，4H)，0.89(m，6H).
Following embodiment 5 is the embodiment that apply in the luminescent layer of organic electroluminescence device containing the iridium organic electroluminescent compounds.
Embodiment 5
The title complex two that the present embodiment makes with embodiment 1 (2 ', 6 '-bis-fluoro-4-methoxyl groups-2,3 '-dipyridyl-N, C
2') (5-(2 '-pyridyl)-1,2, the 4-triazole) close iridium (hereinafter to be referred as (dfpymopy)
2ir (PZ)) organic electroluminescence device made as the doping guest materials of luminescent layer, as shown in Figure 2, the structure of this organic electroluminescence device is the lamination assembling structure, is followed successively by: glass 11/ITO layer 12/PEDOT:PSS layer 13/PVK:(dfpymopy)
2ir (PZ) layer 14/BCP layer 15/Alq
3layer 16/LiF layer 17/Al layer 18; Wherein, PVK is Polyvinyl carbazole; BCP is 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene; PEDOT is 3,4-Ethylenedioxy Thiophene; PSS is polystyrene-sulfonic acid matrix material.
This organic electroluminescence device, under the operating voltage of 9V, the blue light of device emission 465nm, device brightness is 3000cd/m
2.
The manufacture craft of this organic electroluminescence device is as follows:
1, tin indium oxide (ITO) layer that deposition one deck square resistance is 10～20 Ω/mouth on a glass substrate, as transparent anode, thickness is 200nm;
2, by spin coating technique, prepare one deck and play modification PEDOT:PSS layer on ITO, as hole transmission layer, thickness is 30nm;
3, then at PEDOT:PSS layer surface spin coating one deck luminescent layer, thickness is 30nm, and the material of main part of this luminescent layer is PVK, and dopant material is (dfpymopy)
2ir (PZ), i.e. PVK:(dfpymopy)
2ir (PZ) layer; (dfpymopy)
2the doping ratio of Ir (PZ) is 7wt%;
4, on luminescent layer successively vacuum evaporation one deck as the BCP layer (thickness is 10nm) of hole blocking layer, as the Alq3 layer (thickness is 30nm) of electronic injection transport layer with as the LiF (thickness is 1nm) of electronic injection buffer layer;
5, finally adopt vacuum coating technology, metal refining Al layer on buffer layer, thickness is 120nm, as the negative electrode of this organic electroluminescence device.
In case study on implementation 5, under the operating voltage of 9V, the blue light of this organic electroluminescence device emission 465nm, this organic electroluminescence device brightness is 3000cd/m
2.
Due to this organic electroluminescence device owing to containing the iridium organic electroluminescent polymer that purity of color and fluorescence quantum efficiency are higher in luminescent layer; Therefore, it has higher effciency of energy transfer and luminous efficiency, can be widely used in the luminous fields such as blueness or white.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. one kind contains the iridium organic electroluminescent compounds, it is characterized in that, should have following general structural formula containing the iridium organic electroluminescent compounds:
In formula, R is C
1～C
4alkyl.
2. the preparation method containing the iridium organic electroluminescent compounds, is characterized in that, described preparation method comprises the steps:
In S1, oxygen-free environment, by general structure, be
compd A and three hydration iridous chlorides according to mol ratio, within 3: 1～5: 1, add in the first organic solvent, after dissolving, be warming up to the first organic solvent reflux state, reaction generating structure general formula is
two endo compound B; Wherein, R is C
1～C
4alkyl;
In S2, oxygen-free environment, by described two endo compound B and structural formula, be
5-(2 '-pyridyl)-1,2, the 4-triazole adds in the second organic solvent according to mol ratio in 1: 2.5～1: 3.5, then in the second organic solvent, adds the first catalyzer, stirs and is warming up to the second organic solvent reflux state, reaction generating structure general formula is
described containing the iridium organic electroluminescent compounds.
3. the preparation method containing the iridium organic electroluminescent compounds according to claim 2, is characterized in that, in step S1, described compd A is to adopt following step to make:
S11, in the anhydrous and oxygen-free environment, by structural formula, be
compound D and diisopropylamine lithium according to mol ratio, add at 1.2: 1 in tetrahydrofuran solution, under-78 ℃, reacted; Then toward reaction mixture, add trimethyl borate, continue reaction at normal temperatures, the generating structure formula is
compd E;
S12, by described compd E and general structure, be
compound F 17-hydroxy-corticosterone within 1.5: 1～2: 1, add the 3rd organic solvent that contains the second catalyzer according to mol ratio, be warming up under the 3rd organic solvent reflux state and carry out the Suzuki linked reaction, generate described compd A; Wherein, in described compound F 17-hydroxy-corticosterone, R is C
1～C
4alkyl.
4. the preparation method containing the iridium organic electroluminescent compounds according to claim 3, is characterized in that, also comprises the purification step to described compd E in described step S11:
The NaOH aqueous solution that is 5wt% with the quality percentage composition to react in the termination reaction mixed solution; The pH value of the HCl aqueous solution conditioned reaction mixed solution that is then 3N by equivalent concentration is to neutral; Then by ethyl acetate, repeatedly extract rear merging organic phase; Finally concentrate organic phase, obtain the described compd E of purifying.
5. the preparation method containing the iridium organic electroluminescent compounds according to claim 3, is characterized in that, described step S12 also comprises the purification step to described compd A:
Toward containing after adding distilled water in the reaction mixture of described compd A; Then extraction, merge organic phase; Secondly use anhydrous MgSO
4dry organic phase, filter concentrated filtrate; Finally use ethyl acetate and normal hexane mixed solution to make eluent and the filtrate residue is carried out to silica gel column chromatography separate, obtain the described compd A of purifying.
6. the preparation method containing the iridium organic electroluminescent compounds according to claim 3, is characterized in that, in step S12, described catalyzer is K
2cO
3the aqueous solution and Pd (PPh
3)
4mixture; Described K
2cO
310 times of the molar weight molar weight that is described compound F 17-hydroxy-corticosterone, described Pd (PPh
3)
4the molar weight molar weight that is described compound F 17-hydroxy-corticosterone 0.5%.
7. the preparation method containing the iridium organic electroluminescent compounds according to claim 3, is characterized in that, in step S12, described the 3rd organic solvent is tetrahydrofuran (THF), dioxane, toluene or dimethyl sulfoxide (DMSO).
8. the preparation method containing the iridium organic electroluminescent compounds according to claim 2, is characterized in that, in step S1, described the first organic solvent is cellosolvo.
9. the preparation method containing the iridium organic electroluminescent compounds according to claim 2, is characterized in that, in step S2, described the second organic solvent is 1,2-ethylene dichloride, trichloromethane, cellosolvo or tetrahydrofuran (THF); Described the first catalyzer is sodium methylate and silver triflate.
10. an organic electroluminescence device, is characterized in that, the luminescent layer of this organic electroluminescence device comprises containing the iridium organic electroluminescent compounds having following general structure containing the iridium organic electroluminescent compounds:
In formula, R is C
1～C
4alkyl.
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| CN101338193A (en) * | 2008-08-18 | 2009-01-07 | 西安近代化学研究所 | Iridium metal complexes of blue light organic phosphorescent electroluminescent materials |
| WO2010090362A1 (en) * | 2009-02-06 | 2010-08-12 | Pusan National University Industry-University Cooperation Foundation | Phosphorescent light-emitting iridium complex containing pyridyltriazole ligand |
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