CN102532034B - Benzophenanthrene compound containing benzoglioxaline group and application thereof - Google Patents
Benzophenanthrene compound containing benzoglioxaline group and application thereof Download PDFInfo
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- ALBMZCKLJPTAES-UHFFFAOYSA-N Cc(cccc1)c1-c(cccc1)c1[S-](c1ccccc1)c1cc(-[n]2c3ccccc3c3c2cccc3)cc(-[n]2c3ccccc3c3c2cccc3)c1 Chemical compound Cc(cccc1)c1-c(cccc1)c1[S-](c1ccccc1)c1cc(-[n]2c3ccccc3c3c2cccc3)cc(-[n]2c3ccccc3c3c2cccc3)c1 ALBMZCKLJPTAES-UHFFFAOYSA-N 0.000 description 1
- MZYDBGLUVPLRKR-UHFFFAOYSA-N c(cc1)cc(c2ccccc22)c1[n]2-c1cc(-[n]2c3ccccc3c3c2cccc3)ccc1 Chemical compound c(cc1)cc(c2ccccc22)c1[n]2-c1cc(-[n]2c3ccccc3c3c2cccc3)ccc1 MZYDBGLUVPLRKR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a novel compound, which has stable compound property, a simple preparation process, high luminous efficiency and high carrier mobility and can be applied to a phosphorescent main body material and an electron transfer layer of an electroluminescent element. According to an applied device, the driving voltage can be reduced remarkably, and the current efficiency is increased. The structural general formula of the compound is shown as a formula I, wherein a mother nucleus is selected from benzene[c]phenanthrene; Ar is selected from a phenyl group, a biphenylyl group or a naphthyl group; R is alkyl with 1-12 carbon atoms or aryl with 6-30 carbon atoms; m is an integer of 1-2; and n is an integer of 0-1.
Description
Technical field
The present invention relates to a kind of new organic materials, and the application in ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field.
Background technology
Phosphorescent coloring can not, separately as the luminescent layer of OLED, need to be entrained in suitable material of main part usually, forms Subjective and Objective luminescent layer.In order to realize effective transmission ofenergy, usually require the triplet E of material of main part
tbe higher than the triplet E of dye molecule
t.For red or green phosphorescent dye, material of main part CBP (structure is as shown below) conventional at present shows original.But for blue phosphorescent dyes, the triplet energy state of itself is higher, the material of main part finding the more high triplet energy matched with it is just comparatively difficult.For blue phosphorescent dyes FIrpic conventional at present, its triplet is 2.65eV, and the triplet of Common main body CBP is 2.56eV, and the energy transfer process thus between CBP to FIrpic is endothermic process.Research finds, for the phosphorescence guest-host system that endothermic energy transmits, the water oxygen contamination as introduced trace in device fabrication process will cause device efficiency greatly to reduce; And when temperature reduces, endothermic energy transmittance process will be restrained.Meanwhile, energy can not be passed to phosphorescent coloring in time because a large amount of triplet excitons is present in main body, this is also one of reason causing blue phosphorescent device lifetime of short duration.Therefore, the material of main part finding high triplet energy becomes one of main path solving blue phosphorescent device lifetime and efficiency.
From 2003, people are by reducing molecular conjugation degree, design and synthesis mCP, UGH, CDBP, SimCP etc. (structure is shown below) have the material of main part of high triplet energy (2.7-3.2eV), for CBP material of main part, substantially increase the efficiency of blue phosphorescent device.In the work in early stage, we study and report the TBCPF series blue phosphorescent material of main part TBCPF based on carbazole/fluorenyl, there is high triplet energy level and the high stability of 2.84ev, particularly also achieve the high efficiency blue phosphorescent device of wet-layer preparation small molecules individual layer (Tetrahedron, 63 (2007): 10161-10168).Aforementioned body material is the material of main part containing the inclined hole transport ability of carbazole group mostly.At this, we develop again the material of main part with inclined electronic transmission performance.
Summary of the invention
The object of the invention is to propose a kind of novel cpd, this compounds may be used for ORGANIC ELECTROLUMINESCENCE DISPLAYS field.
Benzene [c] phenanthryl group's triplet higher (3.11ev), and the introducing of benzoglyoxaline group or pyridine groups significantly can not reduce the triplet of whole molecule, thus ensures that the triplet of this type of material is enough high.By benzene [c] and phenanthryl group combine with benzoglyoxaline group or pyridine groups, both met phosphorescent light body material particularly blue phosphorescent main body need the requirement of higher triplet, on the other hand because molecule has certain conjugated system, high electron mobility can be provided, be connected with electrophilic pyridine groups, its electronic mobility can be increased, improve material electronics transmission performance.Compound of the present invention has higher electronic transmission performance, good film-forming property, at room temperature has higher stability, and the device applied at room temperature also has higher stability.In organic electroluminescent device, not only can be used as phosphorescent light body material, also can be used as electron transport material.
The present invention discloses a class novel cpd, and its general structure is as follows:
Wherein Ar is selected from phenyl group, biphenyl group or naphthyl group, and R is the alkyl of carbon atom 1-12 or the aryl of carbon atom 6-30, and m is the integer of 1-2, and n is the integer of 0-1
The concrete structure of the Ar in above formula I is selected from following formula:
In order to more clearly demonstrate content of the present invention, lower mask body describes the structure of the compound that the present invention relates to:
Organic materials of the present invention is used as phosphorescence host or electron transfer layer in organic electroluminescence device.
The present invention also proposes a kind of organic electroluminescence device, and its organic function layer comprises above-mentioned general formula compound, and this compounds is as the phosphorescent light body material in organic function layer or electron transport material.
Embodiment
The industrial chemicals such as haloperidid used in the present invention, halogeno-benzene, phenylo boric acid, pyridine boronic acid, naphthalene boronic acids, biphenylboronic acid, benzoglyoxaline, fluorine band oil of mirbane and bromo triphenylene all can have been bought in Chemicals market at home, all available common organic procedures synthesis of pyridine boronic acid of various replacement.
Embodiment
Preparation of compounds carries out linked reaction (Journal of Organometallic Chenistry 1999,576,147-168) mainly through halides and boric acid compound in the present invention.The preparation that wherein boronic acid compounds is see document (Organic Syntheses2005, Vol.81, p.89), be specifically described below:
The preparation of embodiment 1 compound 1-1
11.8g (0.10mmol) benzoglyoxaline is dissolved in 10.1mL triethylamine, drips bromo-iodobenzene 28.1g (0.10mmol) between waiting during zero degree, and stirring at room temperature is warming up to 70-80 DEG C and stirs 2 hours after 30 minutes.With water quencher reaction, dichloromethane extraction, dried over mgso, obtains compd A 23.8g by recrystallizing methanol, is dissolved in by A in dry THF, and-80 DEG C drip normal-butyl reason, stir 15min, then drip triisopropyl boric acid ester.Hydrolysis, regulate pH to neutral precipitation compounds B.20.2g.B and 5,8-dibromobenzene [c] luxuriant and rich with fragrance 1: 1 are carried out linked reaction, and obtained intermediate C, C react with compd E and obtain compound 1-1.With column chromatography purification, eluent is sherwood oil: methylene dichloride=2: 1.MS (m/e): 573, ultimate analysis (C
42h
27n
3): theoretical value C:87.93%, H:4.74%, N:7.32%; Measured value C:88.02%, H:4.77%, N:7.25%.Productive rate 65.7%.
Wherein compd E be prepared as follows shown in figure:
23.5g (0.10mmol) 2,6-dibromo pyridine, 12.0g phenylo boric acid and 0.50g Pd (PPh
3)
4be dissolved in 300.0mL toluene, be dissolved in by 22.0g salt of wormwood in 100.0mL water and add in above reaction solution, 50 DEG C of reaction solutions become yellow immediately.Along with reaction is carried out, reaction solution color is thin out gradually, after 1.5h, adds 2.50g phenylo boric acid, and TLC monitors reaction process.React complete after about 0.5h, organic layer is washed three anhydrous Na
2sO
4carry out column chromatography after drying, eluent is sherwood oil: dichloro=20: 1 (V
1/ V
2) obtain near-white solid D15.1g.MS(m/e)：234。Products obtained therefrom is dissolved in the tetrahydrofuran (THF) of 200.0mL drying, add 16.0 grams of triisopropyl borate esters again and be cooled to-40 DEG C of droppings 34.0mL butyllithium (2.5M), naturally-20 DEG C are warming up to, the hydrochloric acid soln adding 100.0mL1.5M is hydrolyzed, separatory, water layer 10% sodium carbonate solution adjusts pH to neutral, add 40.0g sodium-chlor more saturated, extract with ethyl acetate 40.0mL × 3, merge organic layer, use dried over mgso 30min, elimination siccative, is evaporated to dry, obtains white solid 10.8 grams, MS (m/e): 199, productive rate 84.4%.
Embodiment 2-30, is all similar to embodiment 1, is reacted, can obtain target product by intermediate C from the pyridine boronic acid that different aryl replaces.Specifically be described below:
The synthesis of embodiment 2 compound 1-2
Select intermediate C and 6-phenyl-2-pyridine boronic acid to be raw material, obtain compound 1-2.MS (m/e): 573, ultimate analysis (C
42h
27n
3): theoretical value C:87.93%, H:4.74%, N:7.32%; Measured value C:87.90%, H:4.81%, N:7.29%.Productive rate 61.3%.
The synthesis of embodiment 3 compound 1-3
Select intermediate C and 5-phenyl-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-3.MS (m/e): 573, ultimate analysis (C
42h
27n
3): theoretical value C:87.93%, H:4.74%, N:7.32%; Measured value C:87.88%, H:4.77%, N:7.35%.Productive rate 46.2%.
The synthesis of embodiment 4 compound 1-4
Select intermediate C and 2-phenyl-4-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-4.MS (m/e): 573, ultimate analysis (C
42h
27n
3): theoretical value C:87.93%, H:4.74%, N:7.32%; Measured value C:87.89%, H:4.82%, N:7.29%.Productive rate 42.8%.
The synthesis of embodiment 5 compound 1-5
Select intermediate C and 5-phenyl-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-5.MS (m/e): 573, ultimate analysis (C
42h
27n
3): theoretical value C:87.93%, H:4.74%, N:7.32%; Measured value C:87.82%, H:4.83%, N:7.35%.Productive rate 48.6%.
The synthesis of embodiment 6 compound 1-6
Select intermediate C and 6-phenyl-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-6.MS (m/e): 573, ultimate analysis (C
42h
27n
3): theoretical value C:87.93%, H:4.74%, N:7.32%; Measured value C:87.79%, H:4.81%, N:7.40%.Productive rate 41.3%.
The synthesis of embodiment 7 compound 1-7
Select intermediate C and 6-(3-biphenyl)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-7.MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.82%, H:4.85%, N:6.33%.Productive rate 42.1%.
The synthesis of embodiment 8 compound 1-8
Select intermediate C and 4-(3-biphenyl)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-8.Product MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.78%, H:4.87%, N:6.35%.Productive rate 41.5%.
The synthesis of embodiment 9 compound 1-9
Select intermediate C and 5-(3-biphenyl)-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-9.Product MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.64%, H:4.92%, N:6.44%.Productive rate 44.3%.
The synthesis of embodiment 10 compound 1-10
Select intermediate C and 2-(3-biphenyl)-4-pyridine boronic acid to be the reaction that raw material warp is identical with embodiment 1, obtain compound 1-10.Product MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.66%, H:4.92%, N:6.42%.Productive rate 40.6%.
The synthesis of embodiment 11 compound 1-11
Select intermediate C and 5-(3-biphenyl)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-11.Product MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.80%, H:4.86%, N:6.34%.Productive rate 41.3%.
The synthesis of embodiment 12 compound 1-12
Select intermediate C and 6-(3-biphenyl)-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-12.Product MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.81%, H:4.90%, N:6.29%.Productive rate 43.2%.
The synthesis of embodiment 13 compound 1-13
Select intermediate M and 6-(4-biphenyl)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-13.Product MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.80%, H:4.91%, N:6.29%.Productive rate 45.7%.
The synthesis of embodiment 14 compound 1-14
Select intermediate M and 4-(4-biphenyl)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-14.Product MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.75%, H:4.89%, N:6.36%.Productive rate 41.4%.
The synthesis of embodiment 15 compound 1-15
Select intermediate M and 5-(4-biphenyl)-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-15.Product MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.76%, H:4.83%, N:6.39%.Productive rate 38.8%.
The synthesis of embodiment 16 compound 1-16
Select intermediate M and 2-(4-biphenyl)-4-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-16.Product MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.81%, H:4.77%, N:6.42%.Productive rate 41.6%.
The synthesis of embodiment 17 compound 1-17
Select intermediate M and 5-(4-biphenyl)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 32, obtain compound 1-17.Product MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.60%, H:4.87%, N:6.57%.Productive rate 41.3%.
The synthesis of embodiment 18 compound 1-18
Select intermediate M and 6-(4-biphenyl)-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-18.Product MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.69%, H:4.88%, N:6.43%.Productive rate 42.3%
The synthesis of embodiment 19 compound 1-19
Select intermediate C and 6-(1-naphthalene)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-19.MS (m/e): 623, ultimate analysis (C
46h
29n
3): theoretical value C:88.58%, H:4.69%, N:6.74%; Measured value C:88.65%, H:4.77%, N:6.58%.Productive rate 43.8%.
The synthesis of embodiment 20 compound 1-20
Select intermediate C and 4-(1-naphthalene)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-20.MS (m/e): 623, ultimate analysis (C
46h
29n
3): theoretical value C:88.58%, H:4.69%, N:6.74%; Measured value C:88.62%, H:4.68%, N:6.60%.Productive rate 41.7%.
The synthesis of embodiment 21 compound 1-21
Select intermediate C and 5-(1-naphthalene)-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-21.MS (m/e): 623, ultimate analysis (C
46h
29n
3): theoretical value C:88.58%, H:4.69%, N:6.74%; Measured value C:88.49%, H:4.78%, N:6.73%.Productive rate 43.9%.
The synthesis of embodiment 22 compound 1-22
Select intermediate C and 2-(1-naphthalene)-4-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-22.MS (m/e): 623, ultimate analysis (C
46h
29n
3): theoretical value C:88.58%, H:4.69%, N:6.74%; Measured value C:88.43%, H:4.74%, N:6.83%.Productive rate 40.8%.
The synthesis of embodiment 23 compound 1-23
Be raw material with intermediate C and 5-(1-naphthalene)-2-pyridine boronic acid, through the reaction identical with embodiment 1, obtain compound 1-23.MS (m/e): 623, ultimate analysis (C
46h
29n
3): theoretical value C:88.58%, H:4.69%, N:6.74%; Measured value C:88.45%, H:4.77%, N:6.68%.Productive rate 42.4%.
The synthesis of embodiment 24 compound 1-24
Select intermediate C and 6-(1-naphthalene)-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-24.MS (m/e): 623, ultimate analysis (C
46h
29n
3): theoretical value C:88.58%, H:4.69%, N:6.74%; Measured value C:88.44%, H:4.70%, N:6.86%.Productive rate 41.9%.
The synthesis of embodiment 25 compound 1-25
Select intermediate C and 6-(2-naphthalene)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-25.Product MS (m/e): 623, ultimate analysis (C
46h
29n
3): theoretical value C:88.58%, H:4.69%, N:6.74%; Measured value C:88.47%, H:4.72%, N:6.81%.Productive rate 40.7%.
The synthesis of embodiment 26 compound 1-26
Select intermediate C and 6-(2-naphthalene)-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-26.Product MS (m/e): 623, ultimate analysis (C
46h
29n
3): theoretical value C:88.58%, H:4.69%, N:6.74%; Measured value C:88.64%, H:4.68%, N:6.68%.Productive rate 40.3%.
The synthesis of embodiment 27 compound 1-27
Select intermediate C and 5-(2-naphthalene)-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-27.Product MS (m/e): 623, ultimate analysis (C
46h
29n
3): theoretical value C:88.58%, H:4.69%, N:6.74%; Measured value C:88.55%, H:4.70%, N:6.75%.Productive rate 41.5%.
The synthesis of embodiment 28 compound 1-28
Select intermediate C and 6-(2-naphthalene)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-28.Product MS (m/e): 623, ultimate analysis (C
46h
29n
3): theoretical value C:88.58%, H:4.69%, N:6.74%; Measured value C:88.64%, H:4.71%, N:6.65%.Productive rate 40.8%.
The synthesis of embodiment 29 compound 1-29
Select intermediate C and 5-(2-naphthalene)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-29.Product MS (m/e): 623, ultimate analysis (C
46h
29n
3): theoretical value C:88.58%, H:4.69%, N:6.74%; Measured value C:90.37%, H:4.82%, N:4.81%.Productive rate 40.7%.
The synthesis of embodiment 30 compound 1-30
Select intermediate C and 6-(2-naphthalene)-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 1-30.Product MS (m/e): 623, ultimate analysis (C
46h
29n
3): theoretical value C:88.58%, H:4.69%, N:6.74%; Measured value C:88.55%, H:4.72%, N:6.73%.Productive rate 41.4%.
The synthesis of embodiment 31 compound 1-31
Replace C with compound H, react with 6-phenyl-2-pyridine boronic acid, obtain compound 1-31.
Embodiment 32-60 is similar to embodiment 2-30, is replaced by Compound C H.
The synthesis of embodiment 61 compound 2-1
Select intermediate L and 6-phenyl-2-pyridine boronic acid to react for raw material, through the reaction identical with embodiment 1, obtain compound 2-1.MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.70%, H:4.77%, N:6.53%.Productive rate 46.2% wherein compound K be prepared as follows shown in figure:
The synthesis of embodiment 62 compound 2-2
Select intermediate L and 4-phenyl-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-2.MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.68%, H:4.77%, N:6.55%.Productive rate 44.1%.
The synthesis of embodiment 63 compound 2-3
Select intermediate L and 5-phenyl-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-3.MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.64%, H:4.85%, N:6.51%.Productive rate 43.7%.
The synthesis of embodiment 64 compound 2-4
Select intermediate L and 2-phenyl-4-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-4.MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.75%, H:4.78%, N:6.47%.Productive rate 42.8%.
The synthesis of embodiment 65 compound 2-5
Select intermediate L and 5-phenyl-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-5.MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.66%, H:4.76%, N:6.58%.Productive rate 39.6%.
The synthesis of embodiment 66 compound 2-6
Select intermediate L and 6-phenyl-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-6.MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.79%, H:4.71%, N:6.50%.Productive rate 42.8%.
The synthesis of embodiment 67 compound 2-7
Select intermediate L and 6-(3-biphenyl)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-7.Product MS (m/e): 725, ultimate analysis (C
54h
35n
3): theoretical value C:89.35%, H:4.86%, N:5.79%; Measured value C:89.32%, H:4.81%, N:5.87%.Productive rate 44.6%.
The synthesis of embodiment 68 compound 2-8
Select intermediate L and 4-(3-biphenyl)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-8.Product MS (m/e): 725, ultimate analysis (C
54h
35n
3): theoretical value C:89.35%, H:4.86%, N:5.79%; Measured value C:89.38%, H:4.77%, N:5.85%.Productive rate 41.6%.
The synthesis of embodiment 69 compound 2-9
Select intermediate L and 5-(3-biphenyl)-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 12, obtain compound 2-9.Product MS (m/e): 725, ultimate analysis (C
54h
35n
3): theoretical value C:89.35%, H:4.86%, N:5.79%; Measured value C:89.24%, H:4.88%, N:7.88%.Productive rate 46.3%.
The synthesis of embodiment 70 compound 2-10
Select intermediate L and 2-(3-biphenyl)-4-pyridine boronic acid to be the reaction that raw material warp is identical with embodiment 1, obtain compound 2-10.Product MS (m/e): 725, ultimate analysis (C
54h
35n
3): theoretical value C:89.35%, H:4.86%, N:5.79%; Measured value C:89.31%, H:4.82%, N:5.87%.Productive rate 41.6%.
The synthesis of embodiment 71 compound 2-11
Select intermediate L and 5-(3-biphenyl)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 3-11.Product MS (m/e): 725, ultimate analysis (C
54h
35n
3): theoretical value C:89.35%, H:4.86%, N:5.79%; Measured value C:89.32%, H:4.79%, N:5.89%.Productive rate 41.3%.
The synthesis of embodiment 72 compound 2-12
Select intermediate L and 6-(3-biphenyl)-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 3-12.Product MS (m/e): 725, ultimate analysis (C
54h
35n
3): theoretical value C:89.35%, H:4.86%, N:5.79%; Measured value C:89.33%, H:4.84%, N:5.83%.Productive rate 43.2%.
The synthesis of embodiment 73 compound 2-13
Select intermediate L and 6-(4-biphenyl)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-13.Product MS (m/e): 725, ultimate analysis (C
54h
35n
3): theoretical value C:89.35%, H:4.86%, N:5.79%; Measured value C:89.42%, H:4.78%, N:7.80%.Productive rate 44.7%.
The synthesis of embodiment 74 compound 2-14
Select intermediate L and 4-(4-biphenyl)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-14.Product MS (m/e): 725, ultimate analysis (C
54h
35n
3): theoretical value C:89.35%, H:4.86%, N:5.79%; Measured value C:89.32%, H:4.82%, N:5.86%.Productive rate 42.5%.
The synthesis of embodiment 75 compound 2-15
Select intermediate L and 5-(4-biphenyl)-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-15.Product MS (m/e): 725, ultimate analysis (C
54h
35n
3): theoretical value C:89.35%, H:4.86%, N:5.79%; Measured value C:89.26%, H:4.83%, N:5.91%.Productive rate 39.8%.
The synthesis of embodiment 76 compound 2-16
Select intermediate L and 2-(4-biphenyl)-4-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-16.Product MS (m/e): 725, ultimate analysis (C
54h
35n
3): theoretical value C:89.35%, H:4.86%, N:5.79%; Measured value C:89.44%, H:4.79%, N:5.77%.Productive rate 42.4%.
The synthesis of embodiment 77 compound 2-17
Select intermediate L and 5-(4-biphenyl)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-17.Product MS (m/e): 725, ultimate analysis (C
54h
35n
3): theoretical value C:89.35%, H:4.86%, N:5.79%; Measured value C:89.30%, H:4.85%, N:5.85%.Productive rate 41.9%.
The synthesis of embodiment 78 compound 2-18
Select intermediate L and 6-(4-biphenyl)-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-18.Product MS (m/e): 725, ultimate analysis (C
54h
35n
3): theoretical value C:89.35%, H:4.86%, N:5.79%; Measured value C:89.31%, H:4.78%, N:5.81%.Productive rate 42.3%
The synthesis of embodiment 79 compound 2-19
Select intermediate L and 6-(1-naphthalene)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-19.MS (m/e): 699, ultimate analysis (C
52h
33n
3): theoretical value C:89.24%, H:4.75%, N:6.00%; Measured value C:89.20%, H:4.77%, N:6.03%.Productive rate 42.7%.
The synthesis of embodiment 80 compound 2-20
Select intermediate L and 4-(1-naphthalene)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 3-20.MS (m/e): 699, ultimate analysis (C
52h
33n
3): theoretical value C:89.24%, H:4.75%, N:6.00%; Measured value C:89.22%, H:4.68%, N:6.10%.Productive rate 44.3%.
The synthesis of embodiment 81 compound 2-21
Select intermediate L and 5-(1-naphthalene)-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-21.MS (m/e): 699, ultimate analysis (C
52h
33n
3): theoretical value C:89.24%, H:4.75%, N:6.00%; Measured value C:89.26%, H:4.68%, N:6.16%.Productive rate 41.9%.
The synthesis of embodiment 82 compound 2-22
Select intermediate L and 2-(1-naphthalene)-4-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-22.MS (m/e): 699, ultimate analysis (C
52h
33n
3): theoretical value C:89.24%, H:4.75%, N:6.00%; Measured value C:89.13%, H:4.74%, N:6.03%.Productive rate 40.8%.
The synthesis of embodiment 83 compound 2-23
Be raw material with intermediate L and 5-(1-naphthalene)-2-pyridine boronic acid, through the reaction identical with embodiment 1, obtain compound 2-23.MS (m/e): 699, ultimate analysis (C
52h
33n
3): theoretical value C:89.24%, H:4.75%, N:6.00%; Measured value C:89.25%, H:4.67%, N:6.09%.Productive rate 42.5%.
The synthesis of embodiment 84 compound 2-24
Select intermediate L and 6-(1-naphthalene)-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-24.MS (m/e): 699, ultimate analysis (C
52h
33n
3): theoretical value C:89.24%, H:4.75%, N:6.00%; Measured value C:89.18%, H:4.70%, N:6.12%.Productive rate 41.8%.
The synthesis of embodiment 85 compound 2-25
Select intermediate L and 6-(2-naphthalene)-2-pyridine boronic acid to be raw material, through the three-step reaction identical with embodiment 1, obtain compound 2-25.Product MS (m/e): 699, ultimate analysis (C
52h
33n
3): theoretical value C:89.24%, H:4.75%, N:6.00%; Measured value C:89.30%, H:4.69%, N:5.91%.Productive rate 40.7%.
The synthesis of embodiment 86 compound 2-26
Select intermediate L and 6-(2-naphthalene)-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-26.Product MS (m/e): 699, ultimate analysis (C
52h
33n
3): theoretical value C:89.24%, H:4.75%, N:6.00%; Measured value C:89.34%, H:4.68%, N:5.98%.Productive rate 40.3%.
The synthesis of embodiment 87 compound 2-27
Select intermediate L and 5-(2-naphthalene)-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-27.Product MS (m/e): 699, ultimate analysis (C
52h
33n
3): theoretical value C:89.24%, H:4.75%, N:6.00%; Measured value C:89.25%, H:4.70%, N:6.05%.Productive rate 41.7%.
The synthesis of embodiment 88 compound 2-28
Select intermediate L and 6-(2-naphthalene)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-28.Product MS (m/e): 699, ultimate analysis (C
52h
33n
3): theoretical value C:89.24%, H:4.75%, N:6.00%; Measured value C:89.32%, H:4.71%, N:5.97%.Productive rate 40.8%.
The synthesis of embodiment 89 compound 2-29
Select intermediate L and 5-(2-naphthalene)-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-29.Product MS (m/e): 699, ultimate analysis (C
52h
33n
3): theoretical value C:89.24%, H:4.75%, N:6.00%; Measured value C:89.17%, H:4.78%, N:6.05%.Productive rate 40.7%.
The synthesis of embodiment 90 compound 2-30
Select intermediate L and 6-(2-naphthalene)-3-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-30.Product MS (m/e): 699, ultimate analysis (C
52h
33n
3): theoretical value C:89.24%, H:4.75%, N:6.00%; Measured value C:89.27%, H:4.72%, N:6.01%.Productive rate 41.4%.
The synthesis of embodiment 91 compound 2-31
Select intermediate N and 6-phenyl-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 2-31.Product MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.77%, H:4.82%, N:6.41%.Productive rate 41.4%.Compound M is prepared as follows shown in figure:
Embodiment 92-120; Similarly replace Compound C with embodiment 1 with compound N
The synthesis of embodiment 121 compound 3-1
Select intermediate Q and 6-phenyl-2-pyridine boronic acid and be raw material, through the reaction identical with embodiment 1, obtaining compound 3-1.MS (m/e) 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.81%, H:4.75%, N:6.44%.Productive rate 41.2%.
Wherein compound P be prepared as follows shown in figure:
Embodiment 122-150, replaces intermediate C with intermediate Q, reacts same embodiment 1
The synthesis of embodiment 151 compound 3-31
Select intermediate S and 6-phenyl-2-pyridine boronic acid to be raw material, through the reaction identical with embodiment 1, obtain compound 3-31.MS (m/e): 649, ultimate analysis (C
48h
31n
3): theoretical value C:88.72%, H:4.81%, N:6.47%; Measured value C:88.75%, H:4.75%, N:6.50%.Productive rate 39.7%.
Embodiment 152-180, replaces intermediate C with intermediate S, reacts same embodiment 1
The synthesis of embodiment 181 compound 4-1
Select intermediate H and compound G to be raw material, through twice linked reaction, obtain compound 4-1.MS (m/e): 612, ultimate analysis (C
44h
28n
4): theoretical value C:86.25%, H:4.61%, N:9.14%; Measured value C:86.24%, H:4.71%, N:9.05%.Productive rate 42.4%.
The synthesis of embodiment 182 compound 4-2
Select intermediate C and compd B to be raw material, through twice linked reaction, obtain compound 4-2.MS (m/e): 612, ultimate analysis (C
44h
28n
4): theoretical value C:86.25%, H:4.61%, N:9.14%; Measured value C:86.34%, H:4.63%, N:9.03%.Productive rate 40.3%.
The synthesis of embodiment 183 compound 4-3
Select intermediate C and compound G to be raw material, through twice linked reaction, obtain compound 4-3.MS (m/e): 612, ultimate analysis (C
44h
28n
4): theoretical value C:86.25%, H:4.61%, N:9.14%; Measured value C:86.32%, H:4.63%, N:9.05%.Productive rate 42.7%.
The synthesis of embodiment 184 compound 4-4
Select intermediate N and compound M to be raw material, through twice linked reaction, obtain compound 4-4.MS (m/e): 612, ultimate analysis (C
44h
28n
4): theoretical value C:86.25%, H:4.61%, N:9.14%; Measured value C:86.38%, H:4.70%, N:9.02%.Productive rate 42.4%.
The synthesis of embodiment 185 compound 4-5
Select intermediate L and compound K to be raw material, through twice linked reaction, obtain compound 4-5.MS (m/e): 612, ultimate analysis (C
44h
28n
4): theoretical value C:86.25%, H:4.61%, N:9.14%; Measured value C:86.32%, H:4.66%, N:9.02%.Productive rate 40.3%.
The synthesis of embodiment 186 compound 4-6
Select intermediate L and compound M to be raw material, through twice linked reaction, obtain compound 4-6.MS (m/e): 612, ultimate analysis (C
44h
28n
4): theoretical value C:86.25%, H:4.61%, N:9.14%; Measured value C:86.22%, H:4.70%, N:9.08%.Productive rate 41.5%.
The synthesis of embodiment 187 compound 4-7
Select intermediate S and compound R to be raw material, through twice linked reaction, obtain compound 4-7.MS (m/e): 612, ultimate analysis (C
44h
28n
4): theoretical value C:86.25%, H:4.61%, N:9.14%; Measured value C:86.26%, H:4.71%, N:9.03%.Productive rate 40.9%.
The synthesis of embodiment 188 compound 4-8
Select intermediate Q and compound P to be raw material, through twice linked reaction, obtain compound 4-8.MS (m/e): 612, ultimate analysis (C
44h
28n
4): theoretical value C:86.25%, H:4.61%, N:9.14%; Measured value C:86.22%, H:4.66%, N:9.12%.Productive rate 43.5%.
The synthesis of embodiment 189 compound 4-9
Select intermediate L and compound M to be raw material, through twice linked reaction, obtain compound 4-9.MS (m/e): 612, ultimate analysis (C
44h
28n
4): theoretical value C:86.25%, H:4.61%, N:9.14%; Measured value C:86.17%, H:4.73%, N:9.10%.Productive rate 40.4%.
Here is the Application Example of the compounds of this invention:
Embodiment 190: the preparation of electroluminescence device and result:
The preferred implementation of fabricate devices:
(1) adopt compound of the present invention as the electron transport material in OLED:
Device architecture: ITO/NPB (40nm)/EM1 (30nm)/ETL (the compounds of this invention) (20nm)/LiF (0.5nm)/Al (150nm).Material structure is as shown below:
Device fabrication process is as follows: will be coated with sheet glass supersound process in commercial detergent of ITO transparency conducting layer, rinse in deionized water, at acetone: ultrasonic oil removing in alcohol mixed solvent, be baked under clean environment and remove moisture content completely, by UV-light and ozone clean, and with low energy positively charged ion bundle bombarded surface;
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10
-5~ 9 × 10
-3pa, on above-mentioned anode tunic, vacuum evaporation NPB is as hole transmission layer, and evaporation rate is 0.1nm/s, and evaporation thickness is 40nm;
On hole transmission layer, vacuum evaporation EM1 is as the luminescent layer of device, and evaporation rate is 0.1nm/s, and evaporation total film thickness is 30nm;
Vacuum evaporation on luminescent layer-stratification compound 1-4, the electron transfer layer of 1-8,1-22,1-38,2-4,2-8,2-22,2-38,3-4,3-8,3-22,3-38,4-4,4-7,4-9 device, its evaporation rate is 0.1nm/s, and evaporation total film thickness is 20nm;
At the negative electrode of the upper vacuum evaporation Al layer of electron transfer layer (ETL) as device, thickness is 150nm.
Device performance sees the following form:
Can be seen by upper table, adopt the device of the compounds of this invention relative to adopting the device of the Bphen generally used in the industry and obtain good effect, on the basis that driving voltage reduces relatively, obtain higher luminous efficiency
(2) adopt compound of the present invention as the material of main part of phosphorescence luminescent dye in the luminescent layer of OLED:
Adopt 1-4,1-22,1-38,2-4,2-22,2-38,3-4,3-22,3-38,4-4,4-8 of the present invention as the material of main part of this FIrpic, contrast material of main part mCP.
Device architecture: ITO/NPB (40nm)/TCTA (10nm)/the compounds of this invention: FIrpic (30nm, 10%)/TAZ (40nm)/LiF (0.5nm)/Al (150nm).
Device fabrication process is as follows:
The preparation process of the substrate of device, anode, hole transmission layer and negative electrode is the same.
First hole transmission layer is prepared one deck TCTA as electronic barrier layer, in order to the carrier concentration in balancing device.Then the processing method of double source evaporation is adopted to adopt mCP, compound 1-4 of the present invention respectively, 1-22,1-38,2-4,2-22,2-38,3-4,3-22,3-38,4-4,4-8 is as main body, and adopt FIrpic as the luminescent layer of dyestuff, control evaporation rate is 0.1nm/s, evaporation total film thickness is the doping content of 30nm, FIrpic is 5%.
On luminescent layer, vacuum evaporation one deck TAZ is as the electron transfer layer of device, and its evaporation rate is 0.1nm/s, and evaporation thickness is 40nm.
Vacuum evaporation LiF and Al layer are as the negative electrode of device on the electron transport layer, and thickness is 150nm.
Device performance sees the following form:
Can be seen by upper table, adopt the device of the compounds of this invention to obtain good effect relative to the phosphorescence light emitting device adopting the mCP that generally uses in the industry as material of main part, on the basis that driving voltage reduces relatively, obtain higher current efficiency.
Although describe the present invention in conjunction with the embodiments, the present invention is not limited to above-described embodiment, should be appreciated that, under the guiding of the present invention's design, those skilled in the art can carry out various amendment and improvement, and claims summarise scope of the present invention.
Claims (1)
1. the compound of arbitrary structural formula below is used as the purposes of electron transport layer materials in organic electroluminescence device:
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| CN101868868A (en) * | 2007-11-22 | 2010-10-20 | 出光兴产株式会社 | Organic el element |
| CN102473857A (en) * | 2010-01-15 | 2012-05-23 | 出光兴产株式会社 | Organic electroluminescent element |
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| CN102473857A (en) * | 2010-01-15 | 2012-05-23 | 出光兴产株式会社 | Organic electroluminescent element |
| CN102471269A (en) * | 2010-01-15 | 2012-05-23 | 出光兴产株式会社 | Nitrogen-containing heterocyclic derivative and organic electroluminescent element containing same |
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