CN1931803B - Organic electroluminescent material and its application - Google Patents
Organic electroluminescent material and its application Download PDFInfo
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- CN1931803B CN1931803B CN2006101377566A CN200610137756A CN1931803B CN 1931803 B CN1931803 B CN 1931803B CN 2006101377566 A CN2006101377566 A CN 2006101377566A CN 200610137756 A CN200610137756 A CN 200610137756A CN 1931803 B CN1931803 B CN 1931803B
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Abstract
The present invention is one new type of organic electroluminescent material compound and the organic electroluminescent device with the compound. The compound has the structural generation formula as shown. The organic electroluminescent material has very high film fluorescence quantum yield and film luminescence intensity, and excellent stability and filming performance. The organic electroluminescent material is preferably used as non-doped luminescent material, and may be used as dye doped into other main luminescent material, hole transporting material, electron barrier material, etc.
Description
Technical field
The present invention relates to a kind of small molecules electroluminescent organic material, and the application in organic electroluminescence device, the ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field belonged to.
Background technology
Organic electroluminescence device (hereinafter to be referred as organic EL) has a wide range of applications in various fields owing to have that thin, the full curing of ultralight, luminous, response speed are fast, good temp characteristic, can realize characteristic such as soft demonstration.
The research of organic EL starts from nineteen sixties.People (J.Chem.Phys.1963 such as Pope in 1963,38:2042～2043) studied the blue coloured electroluminous of anthracene single crystal sheet (10～20 μ m), restriction because of the thicker and employed electrode materials of anthracene single crystal luminescent layer (elargol and sodium chloride solution), the luminous trigger voltage of device is up to 400V, and efficient and brightness are all lower.Yet a frontier of luminous science and technology has been opened up in this discovery.Between two more than ten years after this, the progress of organic EL is slow.Until 1987, (Appl.Phys.Lett.1987,51:913～915) such as the C.W.Tang of Kodak just obtained the breakthrough with milestone significance.They adopt bilayer structure to do with oxine aluminium (Alq3) that luminescent layer, aromatic diamines are made hole transmission layer, ITO makes the bi-layer devices that anode, Mg: Ag (10: 1) alloy is made negative electrode, obtains higher quantum yield (1%) and luminous efficiency (1.5lm/W): high brightness (＞1000cd/m2) with than the low driving voltage (device of≤10V.This progress has been aroused the hope that organic EL is applied to panchromatic flat-panel monitor again, and the research of material and device becomes the focus of research rapidly.1988, people such as Adchi [J.Appl.Phys.1988,27 (2): L269～L271] released the multilayer sandwich type structural, have expanded the range of choice of organic EL Material greatly.
Through vicennial development, organic EL Material round Realization red, blue, green emitting, Application Areas has also expanded polymer and metal complex field to from small molecules.In theory, it is ripe that the organic electroluminescent technique of display has been tending towards, and some products come into the market, but in the commercialization process, still have many problems to need to be resolved hurrily.Especially for the various organic materialss of making device, its current carrier injects, transmission performance, material electroluminescence performance, work-ing life, purity of color, between each material and and each electrode between coupling etc., many problems are still unresolved.Simultaneously, material new, that performance is more excellent constantly is found and uses, and element manufacturing technology and device performance are being updated among the raising.
The problem of common De You perylene class, replacement anthracene class, fluorenes class, toluylene-， perylene class blue light materials such as aryl class is its energy level and Alq aspect small molecular blue light material
3Do not match, TBP (2,5,8,11-four uncle Ding Ji perylenes) is doped to has improvement among the BAlq.All there is being report in companies such as Kodak, TDK, Visionox aspect the replacement anthracene class material, and the device color color purity of this type of material is general, and crystallization is difficult for forming amorphous membrance easily.Thermostability, the fluorescence quantum efficiency of fluorenes class material are better, and its device color color purity is general, and synthetic difficulty.Toluylene-aryl (DSA) structure that the emerging product of the bright dipping company of Japan proposes is advantageous, and brightness, efficient, life-span are improved, and respective action mechanism is still being probed into.Micromolecular in addition blue light material also has different structures such as organosilicon, organic boron, makes that the selectable scope of blue light material is more and more wideer.
The basic structure of organic EL device comprises anode/hole injection and transport layer/organic luminous layer/electron injecting layer/negative electrode, now used organic EL device is mostly because driving voltage is higher, luminosity and efficient are lower, and the performance degradation of device get quite fast, so still be difficult to be applied to actual production.
Summary of the invention
The technical problem to be solved in the present invention is to propose a kind of novel electroluminescent material, particularly blue light material, and the luminescent device that adopts this material.
The present invention proposes the compound of the following general formula of a kind of usefulness (1) expression:
X wherein, Y must be in the ortho position or the contraposition of biphenyl key, X ', Y ' be in the biphenyl key between the position, m, n represent the integer of 1-3, p, q represent the integer of 0-2.
In the said structure formula (1), X, Y independently are selected from following general formula (2) or (3) separately:
In the said structure formula (1), X ' and Y ' independently are selected from general formula (2) or (3) separately, perhaps independent separately expression hydrogen atom, perhaps independent separately expression contains the aromatic base of 6-30 carbon atom, contains the aromatic base that condenses of 10-30 carbon atom, contains the fragrant heterocyclic radical of 5-30 carbon atom, the alkyl that contains 1 to 10 carbon atom, the alkoxyl group that contains 1 to 10 carbon atom contains the aralkyl of 6 to 30 carbon atoms, contains the aryloxy of 6 to 30 carbon atoms;
Each substituent R in its formula of (2) and (3)
1, R
2, R
3, R
4And R
5Independent respectively expression hydrogen atom, the aromatic base that contains 6-50 carbon atom, the aromatic base that condenses that contains 10-50 carbon atom, the fragrant heterocyclic radical that contains 5-50 carbon atom, the alkylamino that contains 2 to 50 carbon atoms, the aralkyl that contains 6 to 50 carbon atoms contains the aryloxy of 6 to 50 carbon atoms, contains the fragrant amino of 6 to 50 carbon atoms etc.
In each substituting group in above-mentioned general formula (2) and (3), work as R
1To R
5Can be following group when containing the aromatic base of 6-50 carbon atom: phenyl, o-tolyl, a tolyl, p-methylphenyl, the 2-xenyl, 3-xenyl, 4-xenyl, right-methyl biphenyl, p-terphenyl base, meta-terphenyl base, to tert-butyl-phenyl, the 2,4 difluorobenzene base, right-(1-naphthyl) phenyl, right-(2-naphthyl) phenyl, diphenylethyllene, the triphenylethylene base, p-methoxy-phenyl, Phenoxyphenyl etc.
Work as R
1To R
5For contain 10-50 carbon atom condense aromatic base the time can be following group: 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, the 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, the 4-phenanthryl, 9-phenanthryl, 1-pyrenyl, 2-pyrenyl, the 4-pyrenyl, 1-naphthacenyl, 2-naphthacenyl, 9-naphthacenyl, fluorenyl, benzo (9,10) phenanthryl, fluoranthene base, Qu Ji, 3-methyl-2-naphthyl, 4-methyl isophthalic acid-naphthyl, 4-methyl isophthalic acid-anthryl etc.
Work as R
1To R
5Can be following group when containing the fragrant heterocyclic radical of 5-50 carbon atom: pyrryl, pyridyl, indyl, pseudoindoyl, furyl, benzofuryl, isobenzofuran-base, quinolyl, isoquinolyl, quinoxalinyl, carbazyl, phenanthridinyl, acridyl, phenanthroline base, o-phenanthroline base, phenazinyl, phenothiazinyl ， phenoxazinyl oxazolyl ， oxadiazole base, furazan base, thienyl, benzothienyl, benzothiazolyl, the methylpyrrole base, tertiary butyl pyrryl, skatole base, tertiary butyl indyl, julolidine groups, 1,1,7,7-tetramethyl-julolidine groups etc.
Work as R
1To R
5For the alkylamino that contains 2 to 50 carbon atoms can be following group: N, N-dimethylamino, N, N-diethylamino, N-methyl-N-ethylamino, N, N-dipropyl amino, N, N-dibutylamino, N, N-diamyl amino etc.
Work as R
1To R
5Can be following group when containing the aralkyl of 6 to 50 carbon atoms: phenmethyl, 1-phenylethyl, 2-phenylethyl, 1-propyloxy phenyl base, 2-propyloxy phenyl base, the phenyl tertiary butyl, the Alpha-Naphthyl methyl, 1-Alpha-Naphthyl ethyl, 2-Alpha-Naphthyl ethyl, 1-Alpha-Naphthyl sec.-propyl, 2-Alpha-Naphthyl sec.-propyl, the betanaphthyl methyl, 1-betanaphthyl ethyl, 2-betanaphthyl ethyl, 1-betanaphthyl sec.-propyl, 2-betanaphthyl sec.-propyl, 1-pyrryl methyl, 2-(1-pyrryl) ethyl, right-the methylbenzene methyl, between-the methylbenzene methyl, neighbour-methylbenzene methyl, right-fluorobenzene methyl etc.
Work as R
1To R
5Can be following group when containing the aryloxy of 6 to 50 carbon atoms: phenoxy group, 1-naphthyl oxygen base, 2-naphthyl oxygen base, 1-anthryl oxygen base, 2-anthryl oxygen base, 9-anthryl oxygen base, 1-phenanthryl oxygen base, 2-phenanthryl oxygen base, 3-phenanthryl oxygen base, 4-phenanthryl oxygen base, 9-phenanthryl oxygen base, 1-pyrenyl oxygen base, 2-pyrenyl oxygen base, 4-pyrenyl oxygen base, 2-xenyl oxygen base, 3-xenyl oxygen base, 4-xenyl oxygen base, o-tolyl oxygen base, between tolyl oxygen base, p-methylphenyl oxygen base is to tert-butyl-phenyl oxygen base etc.
Work as R
1To R
5For the fragrant amino that contains 6 to 50 carbon atoms can be following group: N, N-diphenyl amino, N-phenyl-N-tolyl amino, N-phenyl-N-p-methoxy-phenyl amino, N, N-xylyl amino, N, N-diisopropyl phenyl amino, N, N-di-tert-butyl-phenyl amino, N-phenyl-N-naphthyl amino, N-phenyl-N-xenyl amino, N, N-dibiphenylyl amino, N, the N-dinaphthyl amino, N-naphthyl-N-xenyl amino etc.
A kind of organic electroluminescence device comprises anode, negative electrode and organic function layer, and wherein the one deck at least in the organic function layer comprises the compound by following general formula (1) expression of single or blending ingredients:
Wherein X, Y are in the ortho position or the contraposition of biphenyl key, X ', Y ' be in the biphenyl key between the position, m, n represent the integer of 1-3, p, q represent the integer of 0-2;
Described X and Y independently are selected from following general formula (2) or (3) separately;
X ' and Y ' independently are selected from general formula (2) or (3) separately, perhaps independent separately expression hydrogen atom, perhaps independent separately expression contains the aromatic base of 6-30 carbon atom, the aromatic base that condenses that contains 10-30 carbon atom, the fragrant heterocyclic radical that contains 5-30 carbon atom contains the alkyl of 1 to 10 carbon atom, contains the alkoxyl group of 1 to 10 carbon atom, the aralkyl that contains 6 to 30 carbon atoms contains the aryloxy of 6 to 30 carbon atoms;
Each substituent R in general formula (2) and (3)
1, R
2, R
3, R
4And R
5Independent respectively expression hydrogen atom, the aromatic base that contains 6-50 carbon atom, the aromatic base that condenses that contains 10-50 carbon atom, the fragrant heterocyclic radical that contains 5-50 carbon atom, the alkylamino that contains 2 to 50 carbon atoms, the aralkyl that contains 6 to 50 carbon atoms, contain 6 to 50 carbon atoms aryloxy or for the virtue that contains 6 to 50 carbon atoms amino.
For clearer narration content of the present invention, the narration of following mask body but preferred structure in the type of compounds that is not limited to the present invention relates to:
Work as m=1, n=1, p=0, q=0, and X, Y be when being identical group, preferred particular compound C1-C28 is as follows:
Work as m=1, n=1, p=0, q=0, and X, Y be when being different group, preferred particular compound C29-C54 is as follows:
Work as m=1, n=1, p+q=1, and X, Y be when being identical group, preferred particular compound C55-C65 is as follows:
Work as m=1, n=1, p+q=1, and X, Y be when being different group, preferred particular compound C66-C75 is as follows:
Work as m=1, n=1, p+q=2, and X, Y be when being identical group, preferred particular compound C76-C95 is as follows:
Work as m=1, n=1, p+q=2, and X, Y be when being different group, preferred particular compound C96-C103 is as follows:
Work as m+n=3, preferred particular compound C104-C113 is as follows:
Work as m+n=4, preferred particular compound C114-C118 is as follows:
Work as p+q=3-4, preferred particular compound C114-C118 is as follows:
Other preferred Compound C 119-C124 is as follows:
Material of the present invention is parent with biphenyl, ortho position or contraposition at the biphenyl key connect n electronics or πDian Zi group, make the big conjugated system of the whole formation of molecule, but also join dependency group of position between the biphenyl key simultaneously, strengthen this conjugative effect, such structure design has guaranteed that this class material has good luminous property, has good stability and film-forming properties simultaneously owing to suppressed intramolecularly and intermolecular fluorescent quenching.
Electroluminescent organic material of the present invention has very high film fluorescence quantum yield and thin-film light emitting intensity, and the stability and the film forming properties of material are good, such material can preferentially be used as non-doped luminescent material, also can be used as dye adulteratedly in other material of main part and luminous, also can be used as hole transport or electronics blocking material etc. simultaneously.
Utilize the organic electroluminescence device of luminescent material preparation of the present invention can show high purity, high brightness, high efficiency high-performance.
Description of drawings
Fig. 1 is the voltage-to-current density-brightness curve of the device among the embodiment 11;
Fig. 2 is the current density-efficiency curve of the device among the embodiment 11;
Fig. 3 is the emission wavelength curve of the device among the embodiment 11.
Embodiment
The compound of expressing with general formula (1) proposed by the invention generally synthesizes according to the Suzuki linked reaction, adopts the Witting reaction simultaneously, halogenating reaction, and the Ullmann reaction, composite part intermediates such as boration reaction, thus prepare target compound.
Compound with general formula (1) expression proposed by the invention, its synthetic method realizes with reference to the description of following embodiment, but is not limited in following embodiment.
The synthetic embodiment of midbody compound:
Synthesizing of intermediate bromo-derivative
Synthetic embodiment 1 (Synthetic 2,5-dibromo methyl bromobenzene)
Title is to dimethyl bromobenzene 12 grams, and NBS 25.2 restrains the BPO catalytic amount, 60 milliliters in tetracol phenixin is in 250 milliliters of there-necked flasks, and mixture under agitation slowly is warming up to backflow, and the reaction beginning can be observed foam soon and produced, the point plate sees that no longer including raw material reaction can stop, about 2-3 of reaction times hour, and suction filtration, collect filtrate, through column chromatography for separation, eluent is pure sherwood oil, collects end cuts, boil off solvent, obtain white solid 9.25 grams.
Mass spectroscopy products therefrom m/z=342,344 and 340, calculate target product molecular weight C8H7Br3=343, compound is proved to be 2,5-dibromo methyl bromobenzene (productive rate: 42%).
Synthetic embodiment 2 (synthetic N, N-phenylbenzene-3-bromo-4-bromotoluidine)
With reference to the method that synthetic embodiment one describes, raw material N, N-phenylbenzene-3-bromo-4-monomethylaniline (seeing synthetic embodiment five) obtains light yellow solid 8.30 grams.
Mass spectroscopy products therefrom m/z=417,415 and 419, calculate target product molecular weight C19H15Br2N=417, compound is proved to be N, N-phenylbenzene-3-bromo-4-bromotoluidine (productive rate: 47%).
Synthetic embodiment 3 (Synthetic 2,4-dibromo methyl bromobenzene)
With reference to the method that synthetic embodiment one describes, raw material is with 2, and the 4-dimethyl bromobenzene obtains white solid 9.12 grams.
Mass spectroscopy products therefrom m/z=342,344 and 340, calculate target product molecular weight C8H7Br3=343, compound is proved to be 2,4-dibromo methyl bromobenzene (productive rate: 40%).
Synthesizing of intermediate bromo triphenylamine
Synthetic embodiment 4 (synthetic N, N-phenylbenzene-2-bromaniline)
Synthetic according to improved Ullmann reaction, claim the 2-bromaniline 3.3 grams, iodobenzene 8.6 grams, active copper powder 7.2 grams, salt of wormwood 20 grams, 18-hat-6 ethers are an amount of, 80 milliliters of orthodichlorobenzenes in 250 milliliters of there-necked flasks, under nitrogen protection, induction stirring, reflux.The point plate sees that no longer including the reaction of raw material 2-bromaniline can stop, and about 4-5 of reaction times hour, suction filtration was collected filtrate while hot, and through column chromatography for separation, eluent is a sherwood oil: ethyl acetate=10: 1, boil off solvent, and obtain white solid 4.8 grams.
Mass spectroscopy products therefrom m/z=323 and 325 calculates target product molecular weight C18H14BrN=324, and compound is proved to be N, N-phenylbenzene-2-bromaniline (productive rate: 78%).
Synthetic embodiment 5 (synthetic N, N-phenylbenzene-3-bromo-4-monomethylaniline)
With reference to the method that synthetic embodiment four describes, raw material obtains light yellow solid 6.25 grams with 3-bromo-4-monomethylaniline.
Mass spectroscopy products therefrom m/z=337 and 339 calculates target product molecular weight C19H16BrN=338, and compound is proved to be N, N-phenylbenzene-3-bromo-4-monomethylaniline (productive rate: 76%).
Synthetic embodiment 6 (synthetic N, N-two (4-phenyl)-right-bromaniline)
With reference to the method that synthetic embodiment four describes, raw material obtains light yellow solid 5.80 grams with 4-bromaniline and 4-iodine biphenyl.
Mass spectroscopy products therefrom m/z=475 and 477 calculates target product molecular weight C30H22BrN=476, and compound is proved to be N, N-two (4-phenyl)-right-bromaniline (productive rate: 70%).
Synthesizing of intermediate bromo triphenylethylene
Synthetic embodiment 7 (synthesizing 1,1-phenylbenzene-2-(2-bromophenyl) ethene)
Synthetic according to improved Witting reaction, claim 2-brooethyl bromobenzene 3.1 grams, 2.3 milliliters of trimethyl phosphites are in 100 milliliters of single port bottles, assembling prolong and drying tube on the single port bottle, under agitation be warming up to backflow gradually, kept 6-7 hour, after change underpressure distillation into, till the smell of no trimethyl phosphite, obtain thick liquid.
Together with benzophenone 2.2 grams, sodium hydride 1.2 grams (content is in 50%) in 250 milliliters of there-necked flasks of 30 milliliters of addings of the tetrahydrofuran (THF) that drying is handled, under argon shield, prior to stirring 1 hour under the room temperature, are warming up to backflow then with aforesaid liquid, and reaction is spent the night.The point plate is judged reaction process, reduces to room temperature, slowly drips 20 milliliters of anhydrous methanols, stirs to add appropriate amount of deionized water and methylene dichloride after 1-2 hour again, tells organic phase.Through column chromatography for separation, eluent is a sherwood oil: ethyl acetate=50: 1, collect required cut, and suitably concentrate the back placement and can separate out light yellow solid 2.4 grams.
Mass spectroscopy products therefrom m/z=334 and 336 calculates target product molecular weight C20H15Br=335, and compound is proved to be 1,1-phenylbenzene-2-(2-bromophenyl) ethene (productive rate: 60%).
Synthetic embodiment 8 (synthesizing 1,1-phenylbenzene-2-(4-bromophenyl) ethene)
With reference to the method that synthetic embodiment seven describes, raw material obtains light yellow solid 2.8 grams with 4-brooethyl bromobenzene.
Mass spectroscopy products therefrom m/z=334 and 336 calculates target product molecular weight C20H15Br=335, and compound is proved to be 1,1-phenylbenzene-2-(4-bromophenyl) ethene (productive rate: 62%).
Synthetic embodiment 9 (2-(2, the 2-diphenylacetylene)-5-hexichol amido bromobenzene)
With reference to the method that synthetic embodiment seven describes, raw material N, N-phenylbenzene-3-bromo-4-bromotoluidine (seeing synthetic embodiment two) obtains light yellow solid 3.7 grams.
Mass spectroscopy products therefrom m/z=501 and 503 calculates target product molecular weight C32H24BrN=502, and compound is proved to be 2-(2, the 2-diphenylacetylene)-5-hexichol amido bromobenzene (productive rate: 67%).
Synthetic embodiment 10 (Synthetic 2,5-two (2, the 2-diphenylacetylene) bromobenzene)
Synthetic according to improved Witting reaction, claim 2,5-dibromo methyl bromobenzene 5.0 grams (seeing synthetic embodiment one), 5.2 milliliters of trimethyl phosphites are in 100 milliliters of single port bottles, and assembling prolong and drying tube under agitation are warming up to backflow gradually on the single port bottle, kept 6-7 hour, after change underpressure distillation into, till the smell of no trimethyl phosphite, obtain yellow thick liquid.
Together with benzophenone 5.2 grams, sodium hydride 4.0 grams (content is in 50%) in 250 milliliters of there-necked flasks of 50 milliliters of addings of the tetrahydrofuran (THF) that drying is handled, under argon shield, prior to stirring 1 hour under the room temperature, are warming up to backflow then with aforesaid liquid, and reaction is spent the night.The point plate is judged reaction process, reduces to room temperature, slowly drips 30 milliliters of anhydrous methanols, stirs to add appropriate amount of deionized water and methylene dichloride after 1-2 hour again, tells organic phase.Through column chromatography for separation, eluent is a sherwood oil: ethyl acetate=50: 1, collect required cut, and suitably concentrate the back placement and can separate out pale yellow crystals 4.28 grams.
Mass spectroscopy products therefrom m/z=512 and 514 calculates target product molecular weight C34H25Br=513, and compound is proved to be 2,5-two (2, the 2-diphenylacetylene) bromobenzene (productive rate: 57%).
Synthetic embodiment 11 (Synthetic 2,4-two (2, the 2-diphenylacetylene) bromobenzene)
With reference to the method that synthetic embodiment ten describes, raw material is with 2, and 4-dibromo methyl bromobenzene (seeing synthetic embodiment three) obtains light yellow solid 5.23 grams.
Mass spectroscopy products therefrom m/z=512 and 514 calculates target product molecular weight C34H25Br=513, and compound is proved to be 2,4-two (2, the 2-diphenylacetylene) bromobenzene (productive rate: 53%).
Synthesizing of intermediate aryl boric acid
Synthetic embodiment 12 (Synthetic 2-(2, the 2-diphenylacetylene) phenyl-boron dihydroxide)
Method according to conventional boration is synthetic; claim synthetic 1; 1-phenylbenzene-2-(2-bromophenyl) ethene 2.0 grams (seeing synthetic embodiment seven); the tetrahydrofuran (THF) that drying is handled joins in 250 milliliters of there-necked flasks for 20 milliliters together, and under argon shield, stirring and dissolving is a yellow transparent liquid; mixture is chilled to below-64 ℃ with liquid nitrogen; slowly drip the n-Butyl Lithium 3ml (the dropping time surpasses 15min) of 2.5M, be reflected at below-64 ℃ and continue 2 hours, mixture is pale brown look turbid solution.Slowly dripping the new trimethyl borate 2.5ml that steams below-64 ℃, drip the back and be warming up to room temperature naturally, stirring is spent the night.Reaction mixture is chilled to below 10 ℃ with ice bath, and 20 milliliters of the hydrochloric acid solns of dropping 2N stir sufficiently long after the time, use dichloromethane extraction, collect organic phase and evaporate to dryness, washes 1-2 time with sherwood oil heat, and drying obtains white powder 0.98 gram.
Mass spectroscopy products therefrom m/z=300 calculates target product molecular weight C20H17BO2=300, and compound is proved to be 2-(2, the 2-diphenylacetylene) phenyl-boron dihydroxide (productive rate: 52%)
Synthetic embodiment 13 (synthetic 4-(2, the 2-diphenylacetylene) phenyl-boron dihydroxide)
With reference to the method that synthetic embodiment 12 describes, raw material is with 1, and 1-phenylbenzene-2-(4-bromophenyl) ethene (seeing synthetic embodiment eight) obtains white solid 1.0 grams.
Mass spectroscopy products therefrom m/z=300 calculates target product molecular weight C20H17BO2=300, and compound is proved to be 2-(2, the 2-diphenylacetylene) phenyl-boron dihydroxide (productive rate: 53%)
Synthetic embodiment 14 (Synthetic 2-hexichol amido phenyl-boron dihydroxide)
With reference to the method that synthetic embodiment 12 describes, raw material N, N-phenylbenzene-2-bromaniline (seeing synthetic embodiment four) obtains white solid 1.0 grams.
Mass spectroscopy products therefrom m/z=289 calculates target product molecular weight C18H16BNO2=289, and compound is proved to be 2-hexichol amido phenyl-boron dihydroxide (productive rate: 48%)
Synthetic embodiment 15 (Synthetic 2,5-two (2, the 2-diphenylacetylene) phenyl-boron dihydroxide)
Reaction mixture is chilled to below 10 ℃ with ice bath, and 20 milliliters of the hydrochloric acid solns of dropping 2N stir sufficiently long after the time, use dichloromethane extraction, collect organic phase and evaporate to dryness, washes 1-2 time with sherwood oil heat, and drying obtains buff powder 1.43 grams.
Mass spectroscopy products therefrom m/z=478 calculates target product molecular weight C34H27BO2=478, and compound is proved to be 2,5-two (2, the 2-diphenylacetylene) phenyl-boron dihydroxide (productive rate: 48%)
Synthetic embodiment 16 (Synthetic 2,4-two (2, the 2-diphenylacetylene) phenyl-boron dihydroxide)
With reference to the method that synthetic embodiment 15 describes, raw material is with 2, and 4-two (2, the 2-diphenylacetylene) bromobenzene (seeing synthetic embodiment 11) obtains buff powder 1.33 grams.
Mass spectroscopy products therefrom m/z=478 calculates target product molecular weight C34H27BO2=478, and compound is proved to be 2,4-two (2, the 2-diphenylacetylene) phenyl-boron dihydroxide (productive rate: 52%)
Synthetic embodiment 17 (2-(2, the 2-diphenylacetylene)-5-hexichol amido phenyl-boron dihydroxide)
With reference to the method that synthetic embodiment 12 describes, raw material obtains buff powder 1.67 grams with 2-(2, the 2-diphenylacetylene)-5-hexichol amido bromobenzene (seeing synthetic embodiment nine).
Mass spectroscopy products therefrom m/z=467 calculates target product molecular weight C32H26BNO2=467, and compound is proved to be 2-(2, the 2-diphenylacetylene)-5-hexichol amido phenyl-boron dihydroxide (productive rate: 43%)
Be the synthetic embodiment of target compound of the present invention below:
Embodiment one (synthetic compound (C1))
Under argon shield, with 1,1-phenylbenzene-2-(2-bromophenyl) ethene 0.90 gram (seeing synthetic embodiment seven); 2-(2, the 2-diphenylacetylene) phenyl-boron dihydroxide 0.91 gram (seeing synthetic embodiment 12), palladium chloride 0.04 gram; triphenylphosphine 0.12 gram; salt of wormwood 1.4 grams, 20 milliliters of deionized waters, 20 milliliters of dehydrated alcohols; toluene joins in 250 milliliters of there-necked flasks for 30 milliliters together; stir, be heated to backflow, the reaction times is no less than 24 hours.Reaction is told organic phase through column chromatographic isolation and purification after finishing, and obtains yellow solid 1.0 grams.
Mass spectroscopy products therefrom m/z=510 calculates target product molecular weight C40H30=510, and compound is proved to be C1 (productive rate: 80%)
Embodiment two (synthetic compound (C16))
With reference to the method that embodiment one describes, raw material N, N-phenylbenzene-2-bromaniline (seeing synthetic embodiment four) and 2-hexichol amido phenyl-boron dihydroxide (seeing synthetic embodiment 14) obtain buff powder 1.36 grams.
Mass spectroscopy products therefrom m/z=488 calculates target product molecular weight C36H28N2=488, and compound is proved to be C16 (productive rate: 83%)
Embodiment three (synthetic compound (C41))
With reference to the method that embodiment one describes, raw material N, N-phenylbenzene-2-bromaniline (seeing synthetic embodiment four) and 2-(2, the 2-diphenylacetylene) phenyl-boron dihydroxide (seeing synthetic embodiment 12) obtain yellow powder 1.51 grams.
Mass spectroscopy products therefrom m/z=499 calculates target product molecular weight C38H29N=499, and compound is proved to be C41 (productive rate: 70%)
Embodiment four (synthetic compound (C51))
With reference to the method that embodiment one describes, raw material N, N-two (4-phenyl)-right-bromaniline (seeing synthetic embodiment six) and 4-(2, the 2-diphenylacetylene) phenyl-boron dihydroxide (seeing synthetic embodiment 13) obtain yellow powder 1.31 grams.
Mass spectroscopy products therefrom m/z=651 calculates target product molecular weight C50H37N=652, and compound is proved to be C51 (productive rate: 76%)
Embodiment five (synthetic compound (C59))
With reference to the method that embodiment one describes, raw material is with 2, and 5-two (2, the 2-diphenylacetylene) bromobenzene (seeing synthetic embodiment ten) and 4-(2, the 2-diphenylacetylene) phenyl-boron dihydroxide (seeing synthetic embodiment 13) obtain yellow powder 1.89 grams.
Mass spectroscopy products therefrom m/z=688 calculates target product molecular weight C54H40=689, and compound is proved to be C59 (productive rate: 67%)
Embodiment six (synthetic compound (C70))
With reference to the method that embodiment one describes, raw material N, N-two (4-phenyl)-right-bromaniline (seeing synthetic embodiment six) and 2,5-two (2, the 2-diphenylacetylene) phenyl-boron dihydroxide (seeing synthetic embodiment 15) obtains yellow powder 1.39 grams.
Mass spectroscopy products therefrom m/z=829 calculates target product molecular weight C64H47N=830, and compound is proved to be C70 (productive rate: 71%)
Embodiment seven (synthetic compound (C80))
Under argon shield, with 2,5-two (2; the 2-diphenylacetylene) bromobenzene 1.35 grams (seeing synthetic embodiment ten), 2,5-two (2; the 2-diphenylacetylene) phenyl-boron dihydroxide 1.43 grams (seeing synthetic embodiment 15), palladium chloride 0.04 gram, triphenylphosphine 0.12 gram; salt of wormwood 1.4 grams, 20 milliliters of deionized waters, 20 milliliters of dehydrated alcohols; toluene joins in 250 milliliters of there-necked flasks for 30 milliliters together; stir, be heated to backflow, the reaction times is no less than 24 hours.Reaction is told organic phase through column chromatographic isolation and purification after finishing, and obtains glassy yellow solid 1.10 grams.
Mass spectroscopy products therefrom m/z=866 calculates target product molecular weight C68H50=866, and compound is proved to be C80 (productive rate: 49%)
Embodiment eight (synthetic compound (C81))
Method with reference to embodiment seven descriptions, raw material 2-(2, the 2-diphenylacetylene)-and 5-hexichol amido bromobenzene (seeing synthetic embodiment nine) and 2-(2, the 2-diphenylacetylene)-5-hexichol amido phenyl-boron dihydroxide (seeing synthetic embodiment 17), obtain yellow powder 1.79 grams.
Mass spectroscopy products therefrom m/z=844 calculates target product molecular weight C64H48N2=845, and compound is proved to be C81 (productive rate: 52%)
Embodiment nine (synthetic compound (C104))
With reference to the method that embodiment one describes, raw material is with 2, and 4-two (2, the 2-diphenylacetylene) bromobenzene (seeing synthetic embodiment 11) and 4-(2, the 2-diphenylacetylene) phenyl-boron dihydroxide (seeing synthetic embodiment 13) obtain yellow powder 2.01 grams.
Mass spectroscopy products therefrom m/z=688 calculates target product molecular weight C54H40=689, and compound is proved to be C104 (productive rate: 70%)
Embodiment ten (synthetic compound (C114))
With reference to the method that embodiment seven describes, raw material is with 2,4-two (2, the 2-diphenylacetylene) bromobenzene (seeing synthetic embodiment 11) and 2, and 4-two (2, the 2-diphenylacetylene) phenyl-boron dihydroxide (see and synthesize embodiment 16) obtains yellow powder 1.32 and restrains.
Mass spectroscopy products therefrom m/z=866 calculates target product molecular weight C68H50=866, and compound is proved to be C114 (productive rate: 51%)
Be the Application Example of The compounds of this invention below:
The preferred implementation of fabricate devices:
The typical structure of OLED device is: substrate/anode/hole transmission layer (HTL)/organic luminous layer/electron transfer layer (ETL)/negative electrode.
Substrate is transparent, can be glass or flexible substrate, and flexible substrate adopts a kind of material in polyester, the polyimide compounds; Anode layer can adopt inorganic materials or organic conductive polymkeric substance, inorganic materials is generally the higher metals of work function such as metal oxides such as tin indium oxide (hereinafter to be referred as ITO), zinc oxide, zinc tin oxide or gold, copper, silver, the optimized ITO that is chosen as, organic conductive polymkeric substance are preferably a kind of material in Polythiophene/polyvinylbenzenesulfonic acid sodium (hereinafter to be referred as PEDOT:PSS), the polyaniline (hereinafter to be referred as PANI); Cathode layer generally adopts the alloy of the lower metal of work functions such as lithium, magnesium, calcium, strontium, aluminium, indium or they and copper, gold and silver, or the electrode layer that alternately forms of metal and metal fluoride, the present invention is preferably Mg:Ag alloy layer, Ag layer and LiF layer successively, Al layer successively; Hole transmission layer generally adopts the tri-arylamine group material, and the present invention is preferably N, N '-two-(1-naphthyl)-N, N '-phenylbenzene-1,1-xenyl-4,4-diamines (NPB); Electron transfer layer is generally a metal-organic complex, preferably closes gallium (III) (the following Alq that is called for short respectively as three (oxine) aluminium, three (oxine) gallium, (the adjacent amine phenol of salicylidene)-(oxine)
3, Gaq
3, Ga (Saph-q)), also can be the o-phenanthroline class, as 4,7-phenylbenzene-1,10-o-phenanthroline (hereinafter to be referred as Bphen) etc., organic luminous layer generally can adopt small molecule material, can doping fluorescent material or phosphorescent coloring, comprised the luminous organic material that the present invention proposes in the organic luminous layer of the present invention, it can be directly luminous, also can be used as dye adulterated luminously in corresponding material of main part, and preferred material of main part is Alq
3, Gaq
3, Ga (Saph-q).
Prepare a series of organic electroluminescence device of the present invention in accordance with the following methods:
(1) uses clean-out system, deionized water and organic solution to divide several steps to clean and have the anodic glass substrate;
(2) hole transmission layer of the method evaporation device by vacuum-evaporation;
(3) continue the luminescent layer that evaporation comprises red light material of the present invention again;
(4) electron transfer layer of continuation evaporation device;
(5) method by evaporation or sputter prepares metallic cathode again.
Embodiment 11 fabricate devices OLED-1～OLED-2
ITO/NPB(40nm)/C80(15or30nm)/BPhen(40nm)/Mg:Ag/Ag
Preparation OLED-1: sheet glass supersound process in commercial clean-out system that will be coated with the ITO transparency conducting layer, in deionized water, wash, at acetone: ultrasonic oil removing in the alcohol mixed solvent, under clean environment, be baked to and remove moisture content fully, with UV-light cleaning machine irradiation 10 minutes, and with low energy positively charged ion bundle bombarded surface.
The above-mentioned anodic glass substrate that has is placed in the vacuum chamber, be evacuated to 1 * 10
-5～9 * 10
-3Pa continues evaporation NPB as hole transmission layer on above-mentioned anode tunic, evaporation speed is 0.1nm/s, and the evaporation thickness is 40nm;
On hole transmission layer, continue the luminescent layer of evaporation one deck compound of the present invention (C80) as device, its evaporation speed is 0.1nm/s, the evaporation thickness is 15nm;
Continue the electron transfer layer of evaporation one deck BPhen material as device again, its evaporation speed is 0.1nm/s, and the evaporation total film thickness is 40nm;
At last, evaporation Mg:Ag alloy layer and Ag layer are as the cathode layer of device successively on above-mentioned electron transfer layer, and wherein the evaporation speed of Mg:Ag alloy layer is 2.0-3.0nm/s, and thickness is 100nm, and the evaporation speed of Ag layer is 0.3nm/s, and thickness is 100nm.
Preparing OLED-2 according to the method described above, only is that the evaporation thickness that has changed compound (C80) is 30nm, and the performance of device sees table 1 for details:
Table 1:
| Device number | Device architecture is formed | Emission wavelength nm | Open bright voltage V | Brightness cd/m2 | Efficient cd/A |
| OLED-1 | ITO/NPB(40nm)/C80(15nm)/BPhen(40nm)/Mg:Ag/Ag | 468 | 3.27 | 18977 | 3.71 |
| OLED-2 | ITO/NPB(40nm)/C80(30nm)/BPhen(40nm)/Mg:Ag/Ag | 468 | 3.88 | 16426 | 3.0 |
Embodiment 12 fabricate devices OLED-3, OLED-4 and OLED-5
Method just changes the luminescent layer material into C70, C81, C114 respectively with embodiment 11, and the thickness of this layer is respectively 20nm, 25nm and 30nm.The performance of device sees table 2 for details:
Table 2
| Device number | Device architecture is formed | Open bright voltage V | Brightness cd/m2 | Efficient cd/A |
| OLED-3 | ITO/NPB(40nm)/C70(20nm)/BPhen(40nm)/Mg:Ag/Ag | 3.02 | 14520 | 2.3 |
| OLED-4 | ITO/NPB(40nm)/C81(25nm)/BPhen(40nm)/Mg:Ag/Ag | 2.90 | 17523 | 4.2 |
| OLED-5 | ITO/NPB(40nm)/C114(30nm)/BPhen(40nm)/Mg:Ag/Ag | 3.33 | 14000 | 1.9 |
Although describe the present invention in conjunction with the preferred embodiments, but the present invention is not limited to the foregoing description and accompanying drawing, should be appreciated that under the guiding of the present invention's design, those skilled in the art can carry out various modifications and improvement, and claims have been summarized scope of the present invention.
Claims (6)
1. compound, structure is as follows:
2. compound, structure is as follows:
3. compound, shown in the C80 or C81 that structure is following:
4. compound, structure is as follows:
5. compound, structure is as follows:
6. an organic electroluminescence device comprises anode, negative electrode and organic function layer, and wherein the one deck at least in the organic function layer comprises the single compound of being represented by following structural formula:
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| EP3124465B1 (en) * | 2014-07-30 | 2022-09-28 | Merck Patent GmbH | Polymerisable compounds and the use thereof in liquid-crystal displays |
| CN105481672A (en) * | 2015-12-24 | 2016-04-13 | 石家庄诚志永华显示材料有限公司 | Series of fluorescent OLED materials |
| CN106631983B (en) * | 2016-12-23 | 2021-09-21 | 中国科学院长春应用化学研究所 | Dendritic compound based on stilbene unit and organic electroluminescent device |
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