CN102372665A - Aryl compound and application - Google Patents
Aryl compound and application Download PDFInfo
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- CN102372665A CN102372665A CN2010102947559A CN201010294755A CN102372665A CN 102372665 A CN102372665 A CN 102372665A CN 2010102947559 A CN2010102947559 A CN 2010102947559A CN 201010294755 A CN201010294755 A CN 201010294755A CN 102372665 A CN102372665 A CN 102372665A
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- YQQQLYRBDCFYLN-UHFFFAOYSA-N CC(C)(c1c2)c(cc(cc3)-c4cccc(-c5ncccc5)c4)c3-c1ccc2-c1cccc(-c2ccccn2)c1 Chemical compound CC(C)(c1c2)c(cc(cc3)-c4cccc(-c5ncccc5)c4)c3-c1ccc2-c1cccc(-c2ccccn2)c1 YQQQLYRBDCFYLN-UHFFFAOYSA-N 0.000 description 1
- ZJXMSJFJDQVCTR-UHFFFAOYSA-N CC(C)(c1c2)c3cc(-c4cc(-c5cnccc5)ccc4)ccc3-c1ccc2-c1cccc(-c2cccnc2)c1 Chemical compound CC(C)(c1c2)c3cc(-c4cc(-c5cnccc5)ccc4)ccc3-c1ccc2-c1cccc(-c2cccnc2)c1 ZJXMSJFJDQVCTR-UHFFFAOYSA-N 0.000 description 1
Abstract
本发明提供了一种芳基芴类化合物及应用，该化合物结构对称，性质稳定，制备工艺简单，具有较高的发光效率和高的载流子迁移率，可用于电致发光元件的电子传输层。所应用的器件能较明显的降低驱动电压，提高电流效率。该化合物结构通式如下式I所示：其中，母核选自2，7二苯基取代的9，9-二取代基芴，芴的9位取代可以是烷基或者芳基；端基Ar选自吡啶基基团、苯基基团、联苯基基团或者萘基基团；R为碳原子数1-12的烷基或者碳原子数6-30的芳基。 The invention provides an arylfluorene compound and its application. The compound has a symmetrical structure, stable properties, simple preparation process, high luminous efficiency and high carrier mobility, and can be used for electron transport of electroluminescent elements. layer. The applied device can significantly reduce the driving voltage and improve the current efficiency. The general structural formula of the compound is shown in the following formula I: wherein, the core is selected from 9,9-disubstituted fluorene substituted by 2,7 diphenyl, and the 9-position substitution of fluorene can be an alkyl or aryl group; the terminal group Ar It is selected from pyridyl group, phenyl group, biphenyl group or naphthyl group; R is an alkyl group with 1-12 carbon atoms or an aryl group with 6-30 carbon atoms. 
Description
Technical field
The present invention relates to a kind of novel organic compound, and the application in the ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field.
Background technology
The ideal electron transport material should have the characteristic of following several respects: have the reversible electrochemical reducting reaction; HOMO and lumo energy are suitable; Electronic mobility is high; Good film-forming property; Tg is high; Preferably can blocking hole.From the compound structure aspect, require molecule to contain the electron deficiency structural unit, have the good electronic capability of accepting; The molecular weight size to fit can guarantee to have higher second-order transition temperature and be beneficial to the vacuum evaporation film forming again.
As a rule, electron transport material all has the plane aromatics of big conjugated structure, and known well behaved electron transport material is also few at present, and the available electron transport material mainly contains oxine aluminium compounds at present; The furodiazole compound, quinoxaline compound, the polymkeric substance of nitrile group-containing; (Chem.Mater.2004,16,4556-4573 such as other nitrogen-containing heterocycle compound; J Mater.Chem.2005,15,94-106).
Contain the more unitary polymkeric substance of fluorenes and have higher second-order transition temperature more, also have electric transmission character (Chem.Mater.2003,15,1963), but how bad this type of compound dissolution property is, the methods that adopt spin coating more when being used for device.We have prepared one type of new compound that contains fluorene group at this, their symmetrical configuration, and solubleness is high; Preparation technology is simple; Molecular weight is little and possess higher second-order transition temperature, can in vacuum evaporation, form no crystalline membrane uniformly, more is applicable to electroluminescence display device.
Summary of the invention
The objective of the invention is to propose a kind of novel cpd, this compounds can be used for the ORGANIC ELECTROLUMINESCENCE DISPLAYS field.
The rigid planar structure of fluorene derivatives can provide high electronics flowability, and phenyl is connected to its two ends, both can effectively transmit electronics, can reduce the coplanarity of entire compound again.From the cognation aspect of the structure and properties of material, usually with introducing the electron-transporting that drawing electron group can better improve compound in the conjugated system.Phenyl group, xenyl group, pyridyl group and naphthyl group thereof all have the electronic property of drawing, and it is linked to each other with the phenyl fluorenyl, can improve the carrier mobility of compound, make compound that electronic transmission performance preferably arranged.Simultaneously, 9 of fluorenes, thereby introduce on 9 positions stability that substituting group not only improved compound also to a certain degree reduction the planarity of whole molecule improve its film-forming properties.This compounds has stability preferably in air, can be used in the organic electroluminescence device.
The present invention develops a kind of novel organic compound, and this compound is simple for process and have good thermostability, and high electronic mobility can be used in the organic electroluminescence device.
The present invention discloses one type of novel cpd, and its general structure is as follows:
Wherein Ar is selected from pyridyl group, phenyl group, xenyl group or naphthyl group; R is the alkyl of carbonatoms 1-12 or the aryl of carbonatoms 6-30.
R is that alkyl can be selected from methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, n-pentyl, n-hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl etc. in formula I; When R is that aryl can be selected from phenyl, xenyl, naphthyl, anthryl, fluoranthene base, phenanthryl, indenyl, pyrenyl, perylene base etc.
The concrete structure of Ar among the following formula I is selected from Formula Il, III, IV, V, VI, VII, VIII or IX:
In order more to clearly demonstrate content of the present invention, the structure of the compound that following mask body narration the present invention relates to (be that methyl, phenyl, p-methylphenyl are example with R, other is substituted 9,9-two substituted fluorene mode of connection with):
Organic materials of the present invention is used as electron transfer layer in organic electroluminescence device.
The present invention also proposes a kind of organic electroluminescence device, comprises above-mentioned general formula compound in its organic function layer, and this compounds is as the electron transport material in the organic function layer.
Organic materials preparation technology of the present invention is simple, has advantages of higher stability and high electronic mobility, in display of organic electroluminescence, can be used as electron transfer layer.
Embodiment
Used halogeno-benzene, phenylo boric acid, pyridine boric acid, biphenyl boric acid, naphthalene boronic acids and 2 among the present invention; 7-dibrominated-9; 9-dimethyl fluorene, 2; 7-dibrominated-9, basic chemical industry raw materials such as 9-diphenylfluorene all at home Chemicals market bought, all available common organic method of various aryl phenylo boric acids is synthetic.
Embodiment
Compound process in the present invention mainly divided for three steps: (1) is normally through Suzuki linked reaction (Journal of Organometallic Chenistry1999; 576; 147-168) phenylo boric acid, pyridine boric acid, naphthalene boronic acids or biphenyl boric acid and halogenated aryl hydrocarbon are connect, generate single halogenated aryl; (2) with resulting halides in 1 become the aryl phenylo boric acid (Organic Syntheses2004, Vol.10, p.80; Vol.79, p.176 (2002) .); (3) with the boric acid and 2 of gained in 2,7-dibrominated 9, the disubstituted fluorenes coupling of 9-is got up, get final product target molecule.Above-mentioned steps is concrete to be set forth as follows:
Embodiment 1 compound 1-1's is synthetic
(1) the first step
28.3g a bromo-iodobenzene, 12.3g 2-pyridine boric acid and 0.50g Pd (PPh
3)
4Be dissolved in the 300mL toluene, 22.0g salt of wormwood is dissolved in the 100mL water adds in the above reaction solution, add 200mL ethanol again, it is yellow that reaction solution is, and behind 50 ℃ of reaction 1.5h, adds 3.00g 2-pyridine boric acid, TLC monitoring reaction process.About 0.5h afterreaction finishes, with three anhydrous Na of organic layer washing
2SO
4After the drying, revolve to do and use the sherwood oil recrystallization again, get near-white solid 17.40g.MS (m/e): 234, productive rate 74.3%.
(2) second steps
23.4g-bromo-2-pyridine benzene and 24.6 the gram triisopropyl borate esters be dissolved in 200mL exsiccant THF, be cooled to-50 ℃ of Dropwise 5 0mL butyllithiums (2.5M), controlled temperature is between-40 ℃ to-50 ℃.Dropwise and between-40 ℃ to-50 ℃, continue reaction 20 minutes, remove cryostat, be warming up to-20 ℃ naturally; The solution that 20 milliliters of concentrated hydrochloric acids of slow adding and 80 ml waters are made into is hydrolyzed, and rises to room temperature, separatory more naturally; Water layer transfers pH to neutral with 10% sodium carbonate solution, has a large amount of white solids to separate out, and obtains product 15.3 grams after the suction filtration drying; MS (m/e): 199, productive rate 76.8%.
(3) the 3rd steps
7.04g, 2,7-two bromo-9,9-dimethyl fluorene and 12.0g 3-(2-pyridine) phenylo boric acid is dissolved in 400mL YLENE and the 300mL alcoholic acid mixing solutions, adds 13.8g salt of wormwood and 0.5g Pd (PPh
3)
4, behind the backflow 2h, add 2.00g 3-(2-pyridine) phenylo boric acid.The TLC detection reaction finishes, and cooling has been left standstill a large amount of solids and separated out, with its washing three times.Boil twice with THF again.Get white powder 5.10g at last, be compound 1-1.MS (m/e): 500, ultimate analysis (C
37H
28N
2): theoretical value C:88.77%, H:5.64%, N:5.60%; Measured value C:88.80%, H:5.72%, N:5.48%.Productive rate 51.0%.
The preparation route in two steps is all with the preparation of compound 1-1 among the embodiment 1 behind all target molecules; Difference only is the link position and the halo position of phenyl and pyridyl in the first step; This can select different reaction substrates according to concrete target molecule, existing concrete the elaboration as follows:
Embodiment 2 compound 1-2's is synthetic
Selecting a bromo-iodobenzene and 3-pyridine boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-2.Product MS (m/e): 500, ultimate analysis (C
37H
28N
2): theoretical value C:88.77%, H:5.64%, N:5.60%; Measured value C:88.60%, H:5.72%, N:5.68%.Productive rate 26.3%.
Embodiment 3 compound 1-3's is synthetic
Selecting a bromo-iodobenzene and 4-pyridine boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-3.Product MS (m/e): 500, ultimate analysis (C
37H
28N
2): theoretical value C:88.77%, H:5.64%, N:5.60%; Measured value C:88.64%, H:5.75%, N:5.61%.Productive rate is 29.7%.
Embodiment 4 compound 1-4's is synthetic
Selecting a bromo-iodobenzene and phenylo boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-4.Product MS (m/e): 498, ultimate analysis (C
39H
30): theoretical value C:93.94%, H:6.06%; Measured value C:93.78%, H:6.22%.Productive rate 32.5%.
Embodiment 5 compound 1-5's is synthetic
Selecting a bromo-iodobenzene and 3-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-5.Product MS (m/e): 650, ultimate analysis (C
51H
38): theoretical value C:94.12%, H:5.88%; Measured value C:94.01%, H:5.99%.Productive rate 38.2%.
Embodiment 6 compound 1-6's is synthetic
Selecting a bromo-iodobenzene and 4-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-6.Product MS (m/e): 650, ultimate analysis (C
51H
38): theoretical value C:94.12%, H:5.88%; Measured value C:94.31%, H:5.69%.Productive rate 41.0%.
Embodiment 7 compound 1-7's is synthetic
Selecting a bromo-iodobenzene and 1-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-7.Product MS (m/e): 598, ultimate analysis (C
47H
34): theoretical value C:94.28%, H:5.72%; Measured value C:94.12%, H:5.88%.Productive rate 37.4%.
Embodiment 8 compound 1-8's is synthetic
Selecting a bromo-iodobenzene and 2-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-8.Product MS (m/e): 598, ultimate analysis (C
47H
34): theoretical value C:94.28%, H:5.72%; Measured value C:94.37%, H:5.63%.Productive rate 40.1%.
Embodiment 9 compound 1-9's is synthetic
Selecting for use bromo-iodobenzene and 2-pyridine boric acid is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-9.Product MS (m/e): 500, ultimate analysis (C
37H
28N
2): theoretical value C:88.77%, H:5.64%, N:5.60%; Measured value C:88.62%, H:5.82%, N:5.56%.Productive rate 36.3%.
Embodiment 10 compound 1-10's is synthetic
Selecting for use bromo-iodobenzene and 3-pyridine boric acid is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-10.Product MS (m/e): 500, ultimate analysis (C
37H
28N
2): theoretical value C:88.77%, H:5.64%, N:5.60%; Measured value C:88.53%, H:5.87%, N:5.60%.Productive rate 35.8%.
Embodiment 11 compound 1-11's is synthetic
Selecting for use bromo-iodobenzene and 4-pyridine boric acid is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-11.Product MS (m/e): 500, ultimate analysis (C
37H
28N
2): theoretical value C:88.77%, H:5.64%, N:5.60%; Measured value C:88.62%, H:5.85%, N:5.53%.Productive rate 38.2%.
Embodiment 12 compound 1-12's is synthetic
Selecting for use bromo-iodobenzene and phenylo boric acid is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-12.Product MS (m/e): 498, ultimate analysis (C
39H
30): theoretical value C:93.94%, H:6.06%; Measured value C:93.72%, H:6.28%.Productive rate 39.5%.
Embodiment 13 compound 1-13's is synthetic
Selecting for use bromo-iodobenzene and 3-biphenyl boric acid is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-13.Product MS (m/e): 650, ultimate analysis (C
51H
38): theoretical value C:94.12%, H:5.88%; Measured value C:94.17%, H:5.83%.Productive rate 34.9%.
Embodiment 14 compound 1-14's is synthetic
Selecting for use bromo-iodobenzene and 4-biphenyl boric acid is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-14.Product MS (m/e): 650, ultimate analysis (C
51H
38): theoretical value C:94.12%, H:5.88%; Measured value C:94.21%, H:5.79%.Productive rate 40.6%.
Embodiment 15 compound 1-15's is synthetic
Selecting for use bromo-iodobenzene and 1-naphthalene boronic acids is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-15.Product MS (m/e): 598, ultimate analysis (C
47H
34): theoretical value C:94.28%, H:5.72%; Measured value C:94.11%, H:5.89%.Productive rate 38.5%.
Embodiment 16 compound 1-16's is synthetic
Selecting for use bromo-iodobenzene and 2-naphthalene boronic acids is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 1-16.Product MS (m/e): 598, ultimate analysis (C
47H
34): theoretical value C:94.28%, H:5.72%; Measured value C:94.31%, H:5.69%.Productive rate 41.2%.
It is 2 with embodiment 1, the three step selective reaction substrate that compound 2-1 reacts preceding two steps to the embodiment of 2-16,7-dibrominated-9, and the 9-diphenylfluorene, existing concrete the elaboration as follows:
Embodiment 17 compound 2-1's is synthetic
Selecting a bromo-iodobenzene and 2-pyridine boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-1.Product MS (m/e): 624, ultimate analysis (C
47H
32N
2): theoretical value C:90.35%, H:5.16%, N:4.48%; Measured value C:90.42%, H:5.12%, N:4.46%.Productive rate is 29.7%.
Embodiment 18 compound 2-2's is synthetic
Selecting a bromo-iodobenzene and 3-pyridine boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-2.Product MS (m/e): 624, ultimate analysis (C
47H
32N
2): theoretical value C:90.35%, H:5.16%, N:4.48%; Measured value C:90.46%, H:5.10%, N:4.44%.Productive rate 32.3%.
Embodiment 19 compound 2-3's is synthetic
Selecting a bromo-iodobenzene and 4-pyridine boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-3.Product MS (m/e): 624, ultimate analysis (C
47H
32N
2): theoretical value C:90.35%, H:5.16%, N:4.48%; Measured value C:90.31%, H:5.12%, N:4.57%.Productive rate is 34.9%.
Embodiment 20 compound 2-4's is synthetic
Selecting a bromo-iodobenzene and phenylo boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-4.Product MS (m/e): 622, ultimate analysis (C
49H
34): theoretical value C:94.50%, H:5.50%; Measured value C:94.57%, H:5.43%.Productive rate 34.5%.
Embodiment 21 compound 2-5's is synthetic
Selecting a bromo-iodobenzene and 3-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-5.Product MS (m/e): 774, ultimate analysis (C
61H
42): theoretical value C:94.54%, H:5.46%; Measured value C:94.67%, H:5.33%.Productive rate 36.2%.
Embodiment 22 compound 2-6's is synthetic
Selecting a bromo-iodobenzene and 4-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-6.Product MS (m/e): 774, ultimate analysis (C
61H
42): theoretical value C:94.54%, H:5.46%; Measured value C:94.43%, H:5.57%.Productive rate 34.7%.
Embodiment 23 compound 2-7's is synthetic
Selecting a bromo-iodobenzene and 1-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-7.Product MS (m/e): 722, ultimate analysis (C
57H
38): theoretical value C:94.70%, H:5.30%; Measured value C:94.85%, H:5.15%.Productive rate 38.4%.
Embodiment 24 compound 2-8's is synthetic
Selecting a bromo-iodobenzene and 2-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-8.Product MS (m/e): 722, ultimate analysis (C
57H
38): theoretical value C:94.70%, H:5.30%; Measured value C:94.79%, H:5.21%.Productive rate 41.6%.
Embodiment 25 compound 2-9's is synthetic
Selecting for use bromo-iodobenzene and 2-pyridine boric acid is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-9.Product MS (m/e): 624, ultimate analysis (C
47H
32N
2): theoretical value C:90.35%, H:5.16%, N:4.48%; Measured value C:90.27%, H:5.22%, N:4.51%.Productive rate 37.8%.
Embodiment 26 compound 2-10's is synthetic
Selecting for use bromo-iodobenzene and 3-pyridine boric acid is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-10.Product MS (m/e): 624, ultimate analysis (C
47H
32N
2): theoretical value C:90.35%, H:5.16%, N:4.48%; Measured value C:90.27%, H:5.08%, N:4.65%.Productive rate 36.7%.
Embodiment 27 compound 2-11's is synthetic
Selecting for use bromo-iodobenzene and 4-pyridine boric acid is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-11.Product MS (m/e): 624, ultimate analysis (C
47H
32N
2): theoretical value C:90.35%, H:5.16%, N:4.48%; Measured value C:90.48%, H:5.13%, N:4.39%.Productive rate 38.1%.
Embodiment 28 compound 2-12's is synthetic
Selecting for use bromo-iodobenzene and phenylo boric acid is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-12.Product MS (m/e): 622, ultimate analysis (C
49H
34): theoretical value C:94.50%, H:5.50%; Measured value C:94.62%, H:5.38%.Productive rate 39.7%.
Embodiment 29 compound 2-13's is synthetic
Selecting for use bromo-iodobenzene and 3-biphenyl boric acid is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-13.Product MS (m/e): 774, ultimate analysis (C
61H
42): theoretical value C:94.54%, H:5.46%; Measured value C:94.61%, H:5.39%.Productive rate 37.2%.
Embodiment 30 compound 2-14's is synthetic
Selecting for use bromo-iodobenzene and 4-biphenyl boric acid is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-14.Product MS (m/e): 774, ultimate analysis (C
61H
42): theoretical value C:94.54%, H:5.46%; Measured value C:94.48%, H:5.52%.Productive rate 40.3%.
Embodiment 31 compound 2-15's is synthetic
Selecting for use bromo-iodobenzene and 1-naphthalene boronic acids is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-15.Product MS (m/e): 722, ultimate analysis (C
57H
38x): theoretical value C:94.70%, H:5.30%; Measured value C:94.81%, H:5.19%.Productive rate 38.1%.
Embodiment 32 compound 2-16's is synthetic
Selecting for use bromo-iodobenzene and 2-naphthalene boronic acids is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 2-16.Product MS (m/e): 722, ultimate analysis (C
57H
38): theoretical value C:94.70%, H:5.30%; Measured value C:94.75%, H:5.25%.Productive rate 40.7%.
Compound 3-1 is 2 to the preceding two-step reaction of the embodiment of 3-16 with embodiment 1, the three-step reaction substrate, 7-dibrominated-9,9-di-p-tolyl fluorenes, existing concrete the elaboration as follows
Embodiment 33 compound 3-1's is synthetic
Selecting a bromo-iodobenzene and 2-pyridine boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 3-1.Product MS (m/e): 652, ultimate analysis (C
49H
36N
2): theoretical value C:90.15%, H:5.56%, N:4.29%; Measured value C:90.10%, H:5.42%, N:4.48%.Productive rate 35.3%.
Embodiment 34 compound 3-2's is synthetic
Selecting a bromo-iodobenzene and 3-pyridine boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 3-2.Product MS (m/e): 652, ultimate analysis (C
49H
36N
2): theoretical value C:90.15%, H:5.56%, N:4.29%; Measured value C:90.04%, H:5.58%, N:4.38%.Productive rate 34.7%.
Embodiment 35 compound 3-3's is synthetic
Selecting a bromo-iodobenzene and 4-pyridine boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 3-3.Product MS (m/e): 652, ultimate analysis (C
49H
36N
2): theoretical value C:90.15%, H:5.56%, N:4.29%; Measured value C:90.23%, H:5.40%, N:4.37%.Productive rate 37.2%.
Embodiment 36 compound 3-4's is synthetic
Selecting a bromo-iodobenzene and phenylo boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 3-4.Product MS (m/e): 650, ultimate analysis (C
51H
38): theoretical value C:94.12%, H:5.88%; Measured value C:94.03%, H:5.97%.Productive rate 36.5%.
Embodiment 37 compound 3-5's is synthetic
Selecting a bromo-iodobenzene and 3-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 3-5.Product MS (m/e): 802, ultimate analysis (C
63H
46): theoretical value C:94.23%, H:5.77%; Measured value C:94.10%, H:5.90%.Productive rate 38.6%.
Embodiment 38 compound 3-6's is synthetic
Selecting a bromo-iodobenzene and 4-biphenyl boric acid for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 3-6.Product MS (m/e): 802, ultimate analysis (C
63H
46): theoretical value C:94.23%, H:5.77%; Measured value C:94.10%, H:5.90%.Productive rate 38.3%.
Embodiment 39 compound 3-7's is synthetic
Selecting a bromo-iodobenzene and 1-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 3-7.Product MS (m/e): 750, ultimate analysis (C
59H
42): theoretical value C:94.36%, H:5.64%; Measured value C:94.45%, H:5.55%.Productive rate 38.3%.
Embodiment 40 compound 3-8's is synthetic
Selecting a bromo-iodobenzene and 2-naphthalene boronic acids for use is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 3-8.Product MS (m/e): 750, ultimate analysis (C
59H
42): theoretical value C:94.36%, H:5.64%; Measured value C:94.29%, H:5.71%.Productive rate 40.6%.
Embodiment 41 compound 3-9's is synthetic
Selecting for use bromo-iodobenzene and 2-pyridine boric acid is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 3-9.Product MS (m/e): 652, ultimate analysis (C
49H
36N
2): theoretical value C:90.15%, H:5.56%, N:4.29%; Measured value C:90.22%, H:5.45%, N:4.33%.Productive rate 40.6%.
Embodiment 42 compound 3-10's is synthetic
Selecting for use bromo-iodobenzene and 3-pyridine boric acid is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 3-10.Product MS (m/e): 652, ultimate analysis (C
49H
36N
2): theoretical value C:90.15%, H:5..6%, N:4.29%; Measured value C:90.06%, H:5.52%, N:4.42%.Productive rate 37.8%.
Embodiment 43 compound 3-11's is synthetic
Selecting for use bromo-iodobenzene and 4-pyridine boric acid is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 3-11.Product MS (m/e): 652, ultimate analysis (C
49H
36N
2): theoretical value C:90.15%, H:5.56%, N:4.29%; Measured value C:90.12%, H:5.42%, N:4.46%.Productive rate 39.2%.
Embodiment 44 compound 3-12's is synthetic
Selecting for use bromo-iodobenzene and phenylo boric acid is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 3-12.Thing MS (m/e): 650, ultimate analysis (C
51H
38): theoretical value C:94.12%, H:5.88%; Measured value C:94.21%, H:5.79%.Productive rate 39.2%.
Embodiment 45 compound 3-13's is synthetic
Selecting for use bromo-iodobenzene and 3-biphenyl boric acid is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 3-13.Product MS (m/e): 802, ultimate analysis (C
63H
46): theoretical value C:94.23%, H:5.77%; Measured value C:94.14%, H:5.86%.Productive rate 37.9%.
Embodiment 46 compound 3-14's is synthetic
Selecting for use bromo-iodobenzene and 4-biphenyl boric acid is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 3-14.Product MS (m/e): 802, ultimate analysis (C
63H
46): theoretical value C:94.23%, H:5.77%; Measured value C:94.30%, H:5.70%.Productive rate 40.6%.
Embodiment 47 compound 3-15's is synthetic
Selecting for use bromo-iodobenzene and 1-naphthalene boronic acids is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 3-15.Product MS (m/e): 750, ultimate analysis (C
59H
42): theoretical value C:94.36%, H:5.64%; Measured value C:94.41%, H:5.59%.Productive rate 38.5%.
Embodiment 48 compound 3-16's is synthetic
Selecting for use bromo-iodobenzene and 2-naphthalene boronic acids is raw material, and the three-step reaction that warp and embodiment 1 are identical obtains compound 3-16.Product MS (m/e): 750, ultimate analysis (C
59H
42): theoretical value C:94.36%, H:5.64%; Measured value C:94.31%, H:5.69%.Productive rate 40.7%.
Be the application implementation example of The compounds of this invention below:
Embodiment 49: the preparation of electroluminescence device and result
The preferred implementation of fabricate devices:
(1) designs
The transmission performance that compares these electron transport materials for ease; The present invention has designed-simple electroluminescence device (substrate/anode/hole transmission layer (HTL)/organic luminous layer (EL)/electron transfer layer (ETL)/negative electrode); Only use compound 1-1,2-1,2-8 or 3-1 as the electron transport material illustration, efficent electronic transport material Alq
3As comparative material, EM1 is as luminescent material illustration (EM1 is a material of main part, is not luminescent material, and purpose is not to pursue high-level efficiency, but verifies the possibility that these materials are practical).Alq
3With the structure of EM1 be:
Substrate can use the substrate in traditional organic luminescent device, for example: glass or plastics.In element manufacturing of the present invention, select glass substrate for use, ITO makes anode material.
Hole transmission layer can adopt various tri-arylamine group materials.The hole mobile material of in element manufacturing of the present invention, being selected for use is NPB.
Negative electrode can adopt metal and composition thereof structure, like Mg:Ag, Ca:Ag etc., also can be electron injecting layer/metal-layer structure, like LiF/Al, Li
2Common cathode construction such as O.The electronics injecting material of in element manufacturing of the present invention, being selected for use is LiF, and cathode material is Al.
(2) element manufacturing
With the sheet glass that has been coated with ITO transparency conducting layer supersound process in commercial clean-out system; In deionized water, wash, at acetone: ultrasonic oil removing in the alcohol mixed solvent is baked under clean environment and removes moisture content fully; With UV-light and ozone clean, and with low energy positively charged ion bundle bombarded surface;
Place the above-mentioned anodic glass substrate that has in the vacuum chamber, be evacuated to 1 * 10
-5Pa～9 * 10
-3Pa, vacuum evaporation NPB is as hole transmission layer on above-mentioned anode tunic, and vapor deposition speed is 0.1nm/s, and the vapor deposition thickness is 50nm;
Vacuum evaporation EM1 is as the luminescent layer of device on hole transmission layer, and vapor deposition speed is 0.1nm/s, and the vapor deposition total film thickness is 30nm;
Vacuum evaporation one deck compound 1-1,2-1,2-8,3-1 or Alq on luminescent layer
3As the electron transfer layer of device, its vapor deposition speed is 0.1nm/s, and the vapor deposition total film thickness is 50nm;
Go up the negative electrode of vacuum evaporation Al layer as device at electron transfer layer (ETL), thickness is 150nm.
Device performance see the following form (device architecture: ITO/NPB (40nm)/EM1 (30nm)/ETL material (20nm)/LiF (0.5nm)/Al (150nm))
Above result shows that novel organic materials of the present invention can be preferably used as electron transfer layer in organic electroluminescence device.
Although describe the present invention in conjunction with embodiment, the present invention is not limited to the foregoing description, should be appreciated that those skilled in the art can carry out various modifications and improvement under the guiding of the present invention's design, and accompanying claims has been summarized scope of the present invention.
Claims (6)
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