CN102070522A - Quinolone derivatives and application thereof in organic light-emitting devices (OLEDs) - Google Patents
Quinolone derivatives and application thereof in organic light-emitting devices (OLEDs) Download PDFInfo
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- 0 *N(c1ccccc1C=C1)C1=O Chemical compound *N(c1ccccc1C=C1)C1=O 0.000 description 1
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Abstract
The invention discloses quinolone derivatives and preparation method and application thereof. The structural formula of the compounds is shown in the formula I in the specification. As organic light-emitting materials, the compounds can be used for preparing organic light-emitting devices (OLEDs). The OLEDs comprise light-emitting layers, wherein the light-emitting layers contain at least a quinolone derivative to serve as the main material and contain quinolone derivatives or a light-emitting layer formed by the quinolone derivatives, quinolone derivatives or an electron transport layer formed by the quinolone derivatives and quinolone derivatives or a hole blocking layer formed by the quinolone derivatives. The invention further relates to equipment comprising the OLEDs. The quinolone derivatives provided by the invention have appropriate triplet energy levels and obviously improve energy utilization, and when the quinolone derivatives are used for preparing the OLEDs, the prepared devices have satisfactory brightness, current density and efficiency under high current density. The formula I is shown in the specification.
Description
Technical field
The invention belongs to field of organic electroluminescent materials, be specifically related to carbostyril derivative and preparation method thereof, and the purposes of this compounds aspect the preparation organic electroluminescence device.
Background technology
In recent years, the research of white light electroluminescent organic material and device has been subjected to the huge attention of international academic community, government and industrial community, various countries and area are as the numerous and confused great research project (U.S. NextGeneration Lighting Initiative that releases such as the U.S., Europe, Japan, the OLLA of European Union, Japan 21Century Lighting Program) strengthens the research in this field, its reason is: at first, white light organic electroluminescence technology (WOLED) will may be one of most important solid light source technology of new generation with inorganic LED technology together.According to statistics, 20% of the average power consumption of developed country is used for normal lighting, and China's electric consumption on lighting has also accounted for 12% of total electricity consumption, and widely used light source---incandescent light and luminescent lamp electro-optical efficiency are too low at present, and a large amount of electric energy are wasted.A new generation solid light source---its theoretical prediction electro-optical efficiency of WOLED will be present incandescent light and luminescent lamp several times, even more than tens times, the development of this technology and be extensive use of will be significant to save energy and protection environment.Secondly, the development of WOLED technology will drive the progress of relevant flat panel display.At present, although WOLED has obtained Preliminary Applications in coloured plate shows, yet at light source and lighting field, its performance index as efficient and life-span, are far from reaching application requiring, and for this reason, it is very necessary to strengthen the WOLED Study on Technology.
Phosphorescence hybrid combination mode is to realize the new way of efficient WOLED, the difference of this approach and traditional full phosphorescence WOLED maximum is: replace the blue-light-emitting phosphor material with the blue-light-emitting fluorescent material in the device luminescent layer material system, and by the appropriate selection device architecture, make and belong to the luminescent layer material of main part more than 80% because of electricity injects the exciton that forms, and then by energy metastasis difference excitated blue fluorescence and green, the red phosphorescent luminescent material, promptly utilize the energy of singlet state exciton respectively by blue fluorescent material, and it is green, red phosphorescence material is utilized the energy of triplet exciton, but the realization theory internal quantum efficiency reaches 100%.Because this approach makes up blue fluorescent material (comparing with the blue phosphorescent material) and green, the red phosphorescence material of higher stability, high-luminous-efficiency and less bandwidth dexterously, therefore two kinds of dissimilar exciton energies in the capture device respectively still improve in the efficient that improves device and all present very big advantage aspect life-span of device.
In this approach, more requirement has been proposed material of main part.Most of material of main parts itself are not luminous, need the extra suitable blue light dopant material of introducing, and make the device architecture complexity, cost up.Conventional luminous material of main part does not match again aspect triplet energy level, and electric charge injects uneven, and the energy passback is serious, and efficient reduces.
The quinolone group has the higher triplet energy level of 2.86eV, and this structure and tonka bean camphor group have many similaritys, have high chemical stability, and conjugation is easy to characteristics such as chemically modified preferably.But because Carbostyril derivative emission peak positions deflection ultraviolet, fluorescence quantum efficiency is not high simultaneously, and Shang Weijian is with its relevant report as the OLED material of main part.
Summary of the invention
The object of the present invention is to provide a class as carbostyril derivative of electroluminescent organic material and preparation method thereof.This compound has overcome the problem that exists in the present electroluminescent organic material, pass through molecular designing, the substituted radical of introducing rigid structure makes its luminous position red shift to the visible region, improve luminous efficiency, while saboteur's coplanarity, improve the thermostability of compound, to improve its film-forming properties.
The general structure of carbostyril derivative provided by the present invention is suc as formula shown in the I:
Formula I
Wherein,
R
1, R
2, R
3Identical or different, independently representative: hydrogen, fluorine, alkyl, cycloalkyl, substituted alkyl, aralkyl, aryl, heteroaryl, O-alkyl, O-substituted alkyl, O-aryl, O-heteroaryl, N-alkyl, N-substituted aryl, N-aryl, N-heteroaryl, aryl alkenyl or aromatic yl polysulfide yl;
A is organic group arbitrarily, and the preferred fragrance organic group most preferably is preferably the phenyl ring group, carbazole group, anthryl group or fluorene group;
M=0 or 1,
When m=0, n=1 or 2, when m=1, n is the integer more than or equal to 2;
P is 1 or 2, and k gets the positive integer smaller or equal to 4.
R mentioned above
1, R
2, R
3In alkyl be meant alkyl with 1-20 carbon atom, for example: methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl;
Described cycloalkyl is meant the cycloalkyl with 3 to 20 carbon atoms, for example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, adamantyl or norborneol alkyl;
Described substituted alkyl is meant the alkyl with 1-20 carbon atom of replacement, and substituting group can be halogen, hydroxyl, cyano group, amino or nitro, and described halogen is meant fluorine, chlorine, bromine or iodine; For example: methylol, the 1-hydroxyethyl, the 2-hydroxyethyl, 2-hydroxyl isobutyl-, 1, the 2-dihydroxy ethyl, 1,3-dihydroxyl sec.-propyl, 2, the 3 one dihydroxyl-tertiary butyl, 1,2,3 one trihydroxy-propyl group, methyl fluoride, the 1-fluoro ethyl, the 2-fluoro ethyl, 2-fluorine isobutyl-, 1,2-two fluoro ethyls, 1,3-difluoro sec.-propyl, 2, the 3-two fluoro-tertiary butyls, 1,2, the 3-trifluoro propyl, chloromethyl, the 1-chloroethyl, the 2-chloroethyl, 2-chlorine isobutyl-, 1, the 2-Dichloroethyl, 1,3-two chloro isopropyls, 2, the 3-two chloro-tertiary butyls, 1,2,3-three chloropropyls, brooethyl, the 1-bromotrifluoromethane, the 2-bromotrifluoromethane, 2-bromine isobutyl-, 1,2-two bromotrifluoromethanes, 1,3-dibromo sec.-propyl, 2, the 3-two bromo-tertiary butyls, 1,2,3-three bromopropyls, iodomethyl, 1-iodine ethyl, 2-iodine ethyl, 2-iodine isobutyl-, 1,2-diiodo-ethyl, 1,3-diiodo-sec.-propyl, 2, the 3-two iodo-tertiary butyls, 1,2,3-triiodo propyl group, amino methyl, the 1-amino-ethyl, the 2-amino-ethyl, 2-aminoisobutyric base, 1, the 2-diamino ethyl, 1,3-diamino sec.-propyl, 2,3-diamino-tertiary butyl or 1,2,3-triamino propyl group; Cyano methyl, 1-cyano ethyl, 2-cyano ethyl, 2-cyano group isobutyl-, 1,2-dicyano ethyl, 1,3-dicyano sec.-propyl, 2,3-dicyano-tertiary butyl, 1,2,3-tricyano propyl group, nitro methyl, 1-nitro-ethyl, 2-nitro-ethyl, 2-nitro isobutyl-, 1,2-dinitrobenzene ethyl, 1,3-dinitrobenzene sec.-propyl, 2,3-dinitrobenzene-tertiary butyl or 1,2,3-trinitro-propyl group.
Described aralkyl is the alkyl of 1 to 20 carbon atom of aryl replacement, for example: benzyl, the 1-phenylethyl, the 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, to methyl-benzyl, between methyl-benzyl, adjacent methyl-benzyl, p-chlorobenzyl, the m-chloro benzyl, o-chlorobenzyl, to bromobenzyl, between bromobenzyl, adjacent bromobenzyl, to the iodine benzyl, between the iodine benzyl, adjacent iodine benzyl, PAB, between aminobenzyl, adjacent aminobenzyl, to nitrobenzyl, between nitrobenzyl, adjacent nitrobenzyl, to the cyano group benzyl, between the cyano group benzyl, o-cyanobenzyl, 1-chloro-2-propyloxy phenyl base or trityl;
Described aryl is the aryl with 6 to 60 ring carbon atoms, for example phenyl, the 1-naphthyl, the 2-naphthyl, the 1-anthryl, the 2-anthryl, the 9-anthryl, the 1-phenanthryl, the 2-phenanthryl, the 3-phenanthryl, the 4-phenanthryl, the 9-phenanthryl, the 1-naphthacenyl, the 2-naphthacenyl, the 9-naphthacenyl, the 1-pyrenyl, the 2-pyrenyl, the 4-pyrenyl, the 2-xenyl, the 3-xenyl, the 4-xenyl, p-terphenyl-4-base, p-terphenyl-3-base, p-terphenyl-2-base, meta-terphenyl-4-base, meta-terphenyl-3-base, meta-terphenyl-2-base, o-tolyl, between tolyl, p-methylphenyl, to tert-butyl-phenyl, right-(2-phenyl propyl) phenyl, 3-methyl-2-naphthyl, 4-methyl isophthalic acid-naphthyl, 4-methyl isophthalic acid-naphthyl, 4 '-methyl biphenyl or 4 "-tertiary butyl-p-terphenyl-4-base;
Described heteroaryl is the aromatic heterocyclic group with 5 to 50 annular atomses, for example: the 2-pyrryl, the 3-pyrryl, pyridyl, the 2-pyridyl, the 3-pyridyl, the 4-pyridyl, the 2-indyl, the 3-indyl, the 4-indyl, the 5-indyl, the 6-indyl, the 7-indyl, the 1-pseudoindoyl, the 3-pseudoindoyl, the 4-pseudoindoyl, the 5-pseudoindoyl, the 6-pseudoindoyl, the 7-pseudoindoyl, the 2-furyl, the 3-furyl, the 2-benzofuryl, the 3-benzofuryl, the 4-benzofuryl, the 5-benzofuryl, the 6-benzofuryl, the 7-benzofuryl, the 1-isobenzofuran-base, the 3-isobenzofuran-base, the 4-isobenzofuran-base, the 5-isobenzofuran-base, the 6-isobenzofuran-base, the 7-isobenzofuran-base, the 2-quinolyl, the 3-quinolyl, the 4-quinolyl, the 5-quinolyl, the 6-quinolyl, the 7-quinolyl, the 8-quinolyl, the 1-isoquinolyl, the 3-isoquinolyl, the 4-isoquinolyl, the 5-isoquinolyl, the 6-isoquinolyl, the 7-isoquinolyl, the 8-isoquinolyl, the 2-quinoxalinyl, the 5-quinoxalinyl, the 6-quinoxalinyl, the 1-carbazyl, the 2-carbazyl, the 3-carbazyl, the 4-carbazyl, 2-(9H-carbazyl) phenyl, 3-(9H-carbazyl) phenyl, 4-(9H-carbazyl) phenyl, 2-triphen amido, 3-triphen amido, 4-triphen amido, the 1-phenanthridinyl, the 2-phenanthridinyl, the 3-phenanthridinyl, the 4-phenanthridinyl, the 6-phenanthridinyl, the 7-phenanthridinyl, the 8-phenanthridinyl, the 9-phenanthridinyl, the 10-phenanthridinyl, the 1-acridyl, the 2-acridyl, the 3-acridyl, the 4-acridyl, the 9-acridyl, 1, the 7-phenanthrene is coughed up beautiful jade-2-base, 1, the 7-phenanthrene is coughed up beautiful jade-3-base, 1, the 7-phenanthrene is coughed up beautiful jade-4-base, 1, the 7-phenanthrene is coughed up beautiful jade-5-base, 1, the 7-phenanthrene is coughed up beautiful jade-6-base, 1, the 7-phenanthrene is coughed up beautiful jade-8-base, 1, the 7-phenanthrene is coughed up beautiful jade-9-base, 1, the 7-phenanthrene is coughed up beautiful jade-10-base, 1, the 8-phenanthrene is coughed up beautiful jade-2-base, 1, the 8-phenanthrene is coughed up beautiful jade-3-base, 1, the 8-phenanthrene is coughed up beautiful jade-4-base, 1, the 8-phenanthrene is coughed up beautiful jade-5-base, 1, the 8-phenanthrene is coughed up beautiful jade-6-base, 1, the 8-phenanthrene is coughed up beautiful jade-7-base, 1, the 8-phenanthrene is coughed up beautiful jade-9-base, 1, the 8-phenanthrene is coughed up beautiful jade-10-base, 1, the 9-phenanthrene is coughed up beautiful jade-2-base, 1, the 9-phenanthrene is coughed up beautiful jade-3-base, 1, the 9-phenanthrene is coughed up beautiful jade-4-base, 1, the 9-phenanthrene is coughed up beautiful jade-5-base, 1, the 9-phenanthrene is coughed up beautiful jade-6-base, 1, the 9-phenanthrene is coughed up beautiful jade-7-base, 1, the 9-phenanthrene is coughed up beautiful jade-8-base, 1, the 9-phenanthrene is coughed up beautiful jade-10-base, 1, the 10-phenanthrene is coughed up beautiful jade-2-base, 1, the 10-phenanthrene is coughed up beautiful jade-3-base, 1, the 10-phenanthrene is coughed up beautiful jade-4-base, 1, the 10-phenanthrene is coughed up beautiful jade-5-base, 2, the 9-phenanthrene is coughed up beautiful jade-1-base, 2, the 9-phenanthrene is coughed up beautiful jade-3-base, 2, the 9-phenanthrene is coughed up beautiful jade-4-base, 2, the 9-phenanthrene is coughed up beautiful jade-5-base, 2, the 9-phenanthrene is coughed up beautiful jade-6-base, 2, the 9-phenanthrene is coughed up beautiful jade-7-base, 2, the 9-phenanthrene is coughed up beautiful jade 8-base, 2, the 9-phenanthrene is coughed up beautiful jade-10-base, 2, the 8-phenanthrene is coughed up beautiful jade-1-base, 2, the 8-phenanthrene is coughed up beautiful jade-3-base, 2, the 8-phenanthrene is coughed up beautiful jade-4-base, 2, the 8-phenanthrene is coughed up beautiful jade-5-base, 2, the 8-phenanthrene is coughed up beautiful jade-6-base, 2, the 8-phenanthrene is coughed up beautiful jade-7-base, 2, the 8-phenanthrene is coughed up beautiful jade-9-base, 2, the 8-phenanthrene is coughed up beautiful jade-10-base, 2, the 7-phenanthrene is coughed up beautiful jade-1-base, 2, the 7-phenanthrene is coughed up beautiful jade-3-base, 2, the 7-phenanthrene is coughed up beautiful jade-4-base, 2, the 7-phenanthrene is coughed up beautiful jade-5-base, 2, the 7-phenanthrene is coughed up beautiful jade-6-base, 2, the 7-phenanthrene is coughed up beautiful jade-8-base, 2, the 7-phenanthrene is coughed up beautiful jade-9-base, 2, the 7-phenanthrene is coughed up beautiful jade-10-base, the 1-phenazinyl, the 2-phenazinyl, the 1-phenothiazinyl, the 2-phenothiazinyl, the 3-phenothiazinyl, the 4-phenothiazinyl, the 1-phenoxazinyl, the 2-phenoxazinyl, the 3-phenoxazinyl, the 4-phenoxazinyl, the 2-oxazolyl, the 4-oxazolyl, the 5-oxazolyl, 2-oxadiazole base, 5-oxadiazole base, the 3-furyl, the 2-thienyl, the 3-thienyl, the 2-benzothienyl, the 3-benzothienyl, the 4-benzothienyl, the 5-benzothienyl, the 6-benzothienyl, the 7-benzothienyl, the 1-isobenzo-thienyl, the 3-isobenzo-thienyl, the 4-isobenzo-thienyl, the 5-isobenzo-thienyl, the 6-isobenzo-thienyl, the 7-isobenzo-thienyl, 2-methylpyrrole-1-base, 2-methylpyrrole-3-base, 2-methylpyrrole-4-base, 2-methylpyrrole-5-base, 3-methylpyrrole-1-base, 3-methylpyrrole-2-base, 3-methylpyrrole-4-base, 3-methylpyrrole-5-base, 2-tertiary butyl pyrroles-4-base, 3-(2-phenyl propyl) pyrroles-1-base, 2-methyl isophthalic acid-indyl, 4-methyl isophthalic acid-indyl, 2-methyl-3-indyl, 4-methyl-3-indyl, the 2-tertiary butyl-1-indyl, the 4-tertiary butyl-1-indyl, the 2-tertiary butyl-3-indyl or the 4-tertiary butyl-3-indyl;
Described R
1, R
2In aryl alkenyl be the thiazolinyl of 2 to 20 carbon atoms replacing of aryl, the thiazolinyl of 2 to 20 carbon atoms that heteroaryl replaces;
Described R
1, R
2In aromatic yl polysulfide yl be the alkynyl of 2 to 20 carbon atoms replacing of aryl, the alkynyl of 2 to 20 carbon atoms that heteroaryl replaces.
The preparation method of compound shown in the formula I is as follows:
1) compound shown in the formula II and N-bromo-succinimide are reacted in organic solvent, obtain the compound shown in the formula III;
2) under anaerobic and alkaline condition, compound shown in the formula III and organic boronic to be reacted in the solvent that contains the Pd catalyzer, reaction finishes the back and extracts with ether, obtains the Carbostyril derivative shown in the formula I.
(formula II)
(formula III)
Above-mentioned steps 1) be reflected at described under the whipped state and carry out, the temperature of reaction of described reaction is 0-25 ℃, and the reaction times is 5-15 hour.Described organic solvent is selected from following at least a: methylene dichloride, trichloromethane, dimethyl sulfoxide (DMSO), N, dinethylformamide, 1,2-ethylene dichloride, methyl alcohol, ethanol, ether, acetonitrile, acetone, benzene and toluene.
In the described reaction of step 1), the mol ratio of compound shown in the formula II and N-bromo-succinimide is 1: 1-1: 2.
Above-mentioned steps 2) the organic boronic preferred fragrance organic boronic described in is as phenylo boric acid, 2-naphthalene boronic acids, 4-(9-carbazyl) phenylo boric acid etc.
Step 2) be reflected at described under the reflux state and carry out, described temperature of reaction is 80-110 ℃, and preferred 90-100 ℃, the reaction times is 18-48 hour.In the described reaction, the mol ratio of compound shown in the formula III and organic boronic is 1: 2-2: 1.
Step 2) catalyzer of Pd described in specifically can be two (dibenzalacetone) palladium, two (triphenylphosphine) palladium chloride, and four (triphenyl) phosphine palladiums etc. are preferably four (triphenyl) phosphine palladium.
Step 2) alkaline condition in is realized by add basic solution in reaction solvent, described basic solution can be aqueous sodium carbonate, wet chemical, aqueous sodium hydroxide solution or aqueous sodium hydroxide solution etc., the concentration of above-mentioned solution can be 1.5-2.5mol/L, preferred 2mol/L.Described reaction solvent is selected from following at least a: methylene dichloride, trichloromethane, dimethyl sulfoxide (DMSO), N, dinethylformamide, 1,2-ethylene dichloride, ether, acetonitrile, acetone, benzene and toluene.In order to improve productive rate, also can in above-mentioned solvent, add methyl alcohol and/or ethanol.
In resulting mixed solvent, basic solution: reaction solvent: methyl alcohol and/or alcoholic acid volume ratio can be 1: 3-1: 5, and preferred 1: 4: 4.
Described method also comprises step 2) Carbostyril derivative that obtains adopts column chromatography chromatogram or recrystallization method to carry out the step of purifying.
Another object of the present invention provides compound shown in the formula I as the purposes of electroluminescent organic material in the preparation organic electroluminescence device, especially the purposes aspect the preparation organic electro phosphorescent device.
Electroluminescent organic material provided by the present invention can be used as the material of main part of organic electroluminescence device, is used to prepare organic electroluminescence device.Adopting the luminescent device of electroluminescent organic material preparation of the present invention is a kind of extraordinary royal purple light, blue light, green glow, fluorescence, gold-tinted, orange light, ruddiness, near infrared, white light fluorescence and phosphorescence device, especially organic electro phosphorescent device, its good stability and life-span are long.
Described electroluminescent organic material is as the organic luminous layer material of main part of organic electroluminescence device, further relate to the organic electroluminescence device that comprises luminescent layer, this luminescent layer contains at least a Carbostyril derivative as material of main part, and a kind of luminescent layer that contains Carbostyril derivative or form by them, the electron transfer layer that contains Carbostyril derivative or form by them, hole blocking layer that contains Carbostyril derivative or form by them and the equipment that comprises organic electroluminescence device of the present invention.
Described organic electroluminescence device comprises negative electrode, anode and organic thin film layer, at least comprise organic luminous layer in the organic thin film layer between negative electrode and anode, and the organic luminous layer in the organic thin film layer comprises a kind of Carbostyril derivative derivative provided by the present invention at least.
As compound shown in the formula I of the material of main part of organic electroluminescence device can be luminous can be not luminous yet, this compound also can be used as the luminous organic material of organic electroluminescence device, organic electronic transmission and/or hole barrier materials.
Described organic electroluminescence device all has very big purposes in organic transistor, organic integration circuit, organic solar batteries, organic laser, organic sensor or organic electronic label.
Luminescent layer in the described organic electroluminescence device can adopt and be coated with or the method for vacuum evaporation makes, and the structure of device is followed successively by: anode/hole injection layer/hole transmission layer/organic luminous layer/electron transfer layer/electron injecting layer/negative electrode.
The preferred implementation of fabricate devices:
The typical structure of OLED device is: substrate/anode/hole injection layer/hole transmission layer/organic luminous layer/electron transfer layer/electron injecting layer/negative electrode.Substrate is transparent, can be glass or flexible substrate, and flexible substrate adopts a kind of material in polyester or the poly-phthalimide compounds; Anode layer can adopt inorganic materials or organic conductive polymkeric substance, inorganic materials is generally tin indium oxide (hereinafter to be referred as ITO), the higher metals of work function such as metal oxide such as 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 poly-saliva fen/polyvinylbenzenesulfonic acid sodium (hereinafter to be referred as PEDOT:PSS) or the polyaniline (hereinafter to be referred as PANI).Cathode layer generally adopts the lower metal of work functions such as lithium, magnesium, calcium, strontium, aluminium or indium or any and copper, gold or silver-colored alloy in them, and the present invention is preferably the Mg:Ag alloy layer; Hole transmission layer generally adopts the tri-arylamine group material, as N, and N '-two (1-naphthyl)-N, N '-phenylbenzene-1,1-xenyl-4,4-diamines (NPB), 4,4 ', 4 " three (N-carbazole) triphenylamines (TCTA); Electron transfer layer is generally a metal-organic complex, 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)), can be benzimidazoles also, as 1,3,5-three (benzene (TBPI) etc. of 1-phenyl-1H-benzimidazolyl-2 radicals-yl); Hole-injecting material generally adopt CuPc (CuPc) and 4,4 ', 4 " three (N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), the preferred CuPcs of the present invention (CuPc); The electronics injecting material generally adopts inorganic fluoride, as lithium fluoride (LiF), and cesium fluoride (CsF), preferred fluorinated lithium of the present invention (LiF); Organic luminous layer generally can adopt small molecule material, can doping fluorescent material or phosphorescent coloring, comprised the material of main part that the present invention proposes in the organic luminous layer of OLED device of the present invention, it can be directly luminous, can be not luminous yet, preferred dopant material is that three (2-phenylpyridines) close iridium (hereinafter to be referred as Ir (ppy) 3) and three (1-phenyl isoquinolin quinolines) close iridium (hereinafter to be referred as Ir (piq) 3).
Can prepare a series of organic electroluminescence device of the present invention in accordance with the following methods:
(1) divides several steps to clean with clean-out system, deionized water and organic solution and have the anodic glass substrate;
(2) hole injection layer of the method evaporation device by vacuum-evaporation;
(3) hole transmission layer of continuation evaporation device;
(4) luminescent layer of continuation evaporation device;
(5) electron transfer layer of continuation evaporation device;
(6) electron injecting layer of continuation evaporation device;
(7) method by evaporation or sputter prepares metallic cathode again.
The present invention adopts easy method to synthesize a class Carbostyril derivative, and makes the organic light emission layer material with this Carbostyril derivative and made white light parts.This type of Carbostyril derivative has high IP/EA (ionizing potential/electron affinity) value, and has high quantum yield and high brightness, is the luminous material of main part that a class has efficient luminous efficiency; Have high Tg temperature, can suppress the crystalline condition of material effectively, improve film-forming properties, improve the performance of device.With respect to Alq
3(three (oxine) aluminium), the material conjugate length that contains among the present invention increases, and fusing point greatly improves; The most important thing is that the energy utilization significantly improves, thereby has improved the over-all properties of electroluminescent device because material of the present invention possesses suitable triplet energy level.When being used to prepare organic electroluminescence device, obtained gratifying result aspect the efficient of the device of making under brightness, current density and high current density, the over-all properties of the compound (1-methyl-3-(4-(9-carbazyl) phenyl)-4-phenylquinoline-2 (1H)-ketone) of wherein following embodiment 3 preparations obviously is better than the Alq of present widespread use
3Thereby, obtained a kind of organic electroluminescence device of luminous organic material of excellent property.
Description of drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the compound Q 1 of embodiment 1 preparation.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the compound Q 2 of embodiment 2 preparations.
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of the compound Q 3 of embodiment 3 preparations.
Fig. 4 is the mass spectrum of the compound Q 3 of embodiment 3 preparations.
Fig. 5 is the mass spectrum of the compound Q 4 of embodiment 4 preparations.
Fig. 6 is the mass spectrum of the compound Q 5 of embodiment 5 preparations.
Embodiment
Below by specific embodiment, the present invention is further illustrated, but the present invention is not limited thereto.
Experimental technique described in the following embodiment if no special instructions, is ordinary method; Described reagent and material if no special instructions, all can obtain from commercial channels.
All can being prepared of OLED device among the following embodiment according to following method:
Sheet glass supersound process in clean-out system of ITO transparency conducting layer will be coated with, wash in deionized water, at acetone: ultrasonic oil removing in the alcohol mixed solvent is baked under clean environment and removes 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
-5Pa, first evaporation CuPc 15nm on above-mentioned anode tunic continues evaporation NPB as hole transmission layer, and evaporation speed is that 0.1nm/s. evaporation thickness is 30nm;
On hole transmission layer, continue the prepared raw material of evaporation one deck the present invention as luminescent layer, evaporation speed is 0.1nm/s, the evaporation thickness is 15nm;
The prepared raw material of the present invention that continuation evaporation one deck is doped with Compound I r (ppy) 3 is the luminescent layer of material of main part, Ir (ppy) 3 is 1: 100 with the evaporation speed ratio of material of the present invention, the doping content of Ir (ppy) 3 is 5wt%, the total speed of its evaporation is 0.1nm/s, and the evaporation total film thickness is 10nm;
The prepared raw material of the present invention that continuation evaporation one deck is doped with Compound I r (piq) 3 is the luminescent layer of material of main part, Ir (piq) 3 is 1: 100 with the evaporation speed ratio of material of the present invention, the doping content of Ir (piq) 3 is 5wt%, the total speed of its evaporation is 0.1nm/s, and the evaporation total film thickness is 10nm;
Continue the prepared raw material of evaporation one deck the present invention as luminescent layer, evaporation speed is 0.1nm/s, and the evaporation thickness is 15nm;
Continue evaporation TBPI as electron transfer layer, evaporation speed is that 0.1nm/s. evaporation thickness is 30nm;
At last, evaporation LiF layer and Mg:Ag alloy layer are as the cathode layer of device on above-mentioned electron transfer layer, and wherein the thickness of LiF layer is 0.5nm, and the evaporation speed of Mg:Ag alloy layer is 2.0～3.0nm/s, and thickness is 100nm.
Brightness and tristimulus coordinates are measured by the PR650 spectrophotometer among the following embodiment, and current density-voltage curve is measured by Keithley 2400 digital source tables.Above-mentioned instrument all is connected by program with computer controls test.Voltage when opening bright voltage and being 1cd/m2, luminous efficiency convert via brightness/current density and obtain.
The first step: get mol ratio and be 1-methyl-4-phenylquinoline-2 (1H)-ketone of 1: 1, the N-bromo-succinimide is a raw material, above-mentioned raw materials is dissolved in N, dinethylformamide, stirring at room reaction 10 hours adds elutriation and goes out a large amount of solids, the washing solid, drying promptly gets corresponding bromo-derivative, productive rate 80%.
Second step: under nitrogen protection; bromo-derivative and phenylo boric acid (mol ratio is 1: 1) that the first step is obtained drop in the two-mouth bottle; four (triphenyl) phosphine palladium that adds catalytic amount) and mixed solvent (sodium carbonate solution (2mol/L): toluene: ethanol=1: 4: 4); keep 90-100 ℃ of temperature; stirred 24 hours, extracted with diethyl ether, (elutriant is petrol ether/ethyl acetate=3/1 to product through column chromatography; collection Rf=0.7 component) obtains high purity target product (Q1), productive rate about 50%.
The structural identification data:
MS：311.1311。
The OLED device preparation of compound Q 1
Device architecture: anode/hole injection layer/hole transmission layer/organic luminous layer/organic luminous layer/organic luminous layer/organic luminous layer/electron transfer layer/electron injecting layer/negative electrode
ITO/CuPc/NPB(30nm)/Q?1(15nm)/Q1：
5％Ir(ppy)
3(10nm)/Q1：5％Ir(piq)
3(10nm)/Q1(15nm)/TPBI(30nm)/LiF/Mg:Ag
The device performance index is as follows:
Tristimulus coordinates: (0.41,0.42);
Play bright voltage: 3.5V;
High-high brightness: 15800cd/m2 (12V);
Luminous efficiency: 14.5cd/A.
The preparation of embodiment 2,1-methyl-3-(2-naphthyl)-4-phenylquinoline-2 (1H)-ketone (Q2)
The first step: get mol ratio and be 1-ethyl-4-phenylquinoline-2 (1H)-ketone of 1: 1, the N-bromo-succinimide is a raw material, and above-mentioned raw materials is dissolved in N, dinethylformamide, stirring at room 10 hours adds elutriation and goes out a large amount of solids, the washing solid, drying promptly gets corresponding bromo-derivative, productive rate 80%.
Second step: under nitrogen protection; product and 2-naphthalene boronic acids (mol ratio is 1: 1) that the first step is obtained drop in the two-mouth bottle; four (triphenyl) phosphine palladium that adds catalytic amount) and mixed solvent (sodium carbonate solution (2mol/L): toluene: ethanol=1: 4: 4); keep 90-100 ℃ of temperature; stirred 24 hours, extracted with diethyl ether, (elutriant is petrol ether/ethyl acetate=3/1 to product through column chromatography; collection Rf=0.6 component) obtains high purity target product (Q2), productive rate about 50%.
The structural identification data:
MS：375.1525
The OLED device preparation of compound Q 2
Have the compound of structural formula Q1 except the compound with above-mentioned structural formula Q2 substitutes, prepared OLED device architecture is with embodiment 1.
The device performance index is as follows:
Tristimulus coordinates: (0.42,0.42);
Play bright voltage: 3.5V;
High-high brightness: 16800cd/m2 (12V);
Luminous efficiency: 13.5cd/A.
The preparation of embodiment 3,1-methyl-3-(4-(9-carbazyl) phenyl)-4-phenylquinoline-2 (1H)-ketone (Q3)
The first step: get mol ratio and be 1-methyl-4-phenylquinoline-2 (1H)-ketone of 1: 1, the N-bromo-succinimide is a raw material, and above-mentioned raw materials is dissolved in N, dinethylformamide, stirring at room 10 hours adds elutriation and goes out a large amount of solids, the washing solid, drying promptly gets corresponding bromo-derivative, productive rate 80%.
Second step: under nitrogen protection; product and 4-(9-carbazyl) phenylo boric acid (mol ratio is 1: 1) that the first step is obtained drop in the two-mouth bottle; four (triphenyl) phosphine palladium that adds catalytic amount) and mixed solvent (sodium carbonate solution: toluene: ethanol=1: 4: 4); keep 90-100 ℃ of temperature; stirred 24 hours, extracted with diethyl ether, (elutriant is petrol ether/ethyl acetate=3/1 to product through column chromatography; collection Rf=0.7 component) obtains high purity target product (Q3), productive rate about 50%.
The structural identification data:
MS：476.6417。
The OLED device preparation of compound Q 3
Have the compound of structural formula Q1 except the compound with above-mentioned structural formula Q3 substitutes, prepared OLED device architecture is with embodiment 1.
The device performance index is as follows:
Tristimulus coordinates: (0.43,0.43);
Play bright voltage: 3.2V;
High-high brightness: 19800cd/m2 (12V);
Luminous efficiency: 17.3cd/A.
Embodiment 4,1-methyl-3, the preparation of 6-two (2-naphthyl)-4-phenylquinoline-(2H)-ketone (Q4)
The first step: 1-methyl-4-phenylquinoline-2 (1H)-ketone, the N-bromo-succinimide getting mol ratio and be 1: 2 are raw material, above-mentioned raw materials are dissolved in methylene dichloride, stirring at room 10 hours, add elutriation and go out a large amount of solids, washing solid, drying, promptly get corresponding bromo-derivative, productive rate 80%.
Second step: under nitrogen protection; product and 2-naphthalene boronic acids (mol ratio is 1: 2) that the first step is obtained drop in the two-mouth bottle; four (triphenyl) phosphine palladium that adds catalytic amount) and mixed solvent (solution of potassium carbonate: toluene: methyl alcohol=1: 4: 4); keep 90-100 ℃ of temperature; stirred 24 hours, extraction, product is through column chromatography chromatogram or recrystallization; obtain high purity target product (Q4), productive rate about 50%.
The structural identification data:
MS：487.5815。
The OLED device preparation of compound Q 4
Device architecture: anode/hole injection layer/hole transmission layer/organic luminous layer/organic luminous layer/organic luminous layer/organic luminous layer/electron transfer layer/electron injecting layer/negative electrode
ITO/CuPc/NPB(15nm)/Q4(15nm)/Q4：
5％Ir(ppy)
3(10nm)/Q4：5％Ir(piq)
3(10nm)/Q4(15nm)/TPBI(30nm)/LiF/Mg:Ag
The device performance index is as follows:
Tristimulus coordinates: (0.41,0.42);
Play bright voltage: 3.5V;
High-high brightness: 15300cd/m2 (12V);
Luminous efficiency: 14.4cd/A.
The preparation of embodiment 5,1-methyl-3-(4-(3-(1-methyl-4 phenylquinoline-2 (1H)-ketone))) phenyl-4-phenylquinoline-2 (1H)-ketone (Q5)
The first step: get mol ratio and be 1-methyl-4-phenylquinoline-2 (1H)-ketone of 1: 1, the N-bromo-succinimide is a raw material, and above-mentioned raw materials is dissolved in N, dinethylformamide, stirring at room 10 hours adds elutriation and goes out a large amount of solids, the washing solid, drying, both corresponding bromo-derivative, productive rate 80%.
Second step: under nitrogen protection; the product and 1 that the first step is obtained; the two boric acid (mol ratio is 2: 1) of 2-benzene drop in the two-mouth bottle; four (triphenyl) phosphine palladium that adds catalytic amount) and mixed solvent (solution of potassium carbonate: toluene: methyl alcohol=1: 4: 4), 90-100 ℃ of maintenance temperature stirred 24 hours; extracted with diethyl ether; the product ethyl alcohol recrystallization obtains high purity target product (Q5), productive rate about 50%.
The structural identification data:
MS＝544.2057
The OLED device preparation of compound Q 5
Device architecture: have the compound of structural formula Q4 except the compound with above-mentioned structural formula Q5 substitutes, prepared OLED device architecture is with embodiment 4.
The device performance index is as follows:
Tristimulus coordinates: (0.41,0.42);
Play bright voltage: 3.5V;
High-high brightness: 19800cd/m2 (12V);
Luminous efficiency: 14.5cd/A.
Embodiment 6, the 1-methyl-3-(preparation of 6-(3-(3-(1,2-dihydro-1-methyl-2-carbonyl-4-phenylquinoline ketone))-9-phenyl carbazole)-4-phenylquinoline-2 (1H)-ketone (Q6)
The first step: get mol ratio and be 1-methyl-4-phenylquinoline-2 (1H)-ketone of 1: 2, the N-bromo-succinimide is a raw material, and above-mentioned raw materials is dissolved in N, dinethylformamide, stirring at room 10 hours adds elutriation and goes out a large amount of solids, the washing solid, drying, both corresponding bromo-derivative, productive rate 80%.
Second step: under nitrogen protection; the product and 3 that the first step is obtained; the two boric acid (mol ratio is 1: 2) of 6-(9-phenyl) carbazole drop in the two-mouth bottle; four (triphenyl) phosphine palladium that adds catalytic amount) and mixed solvent (sodium carbonate solution: toluene: methyl alcohol=1: 4: 4), 90-100 ℃ of maintenance temperature stirred 24 hours; extraction; the product ethyl alcohol recrystallization obtains high purity target product (Q6), productive rate about 50%.
The structural identification data:
MS：709.2722
The OLED device preparation of compound Q 6
Have the compound of structural formula Q4 except the compound with above-mentioned structural formula Q6 substitutes, prepared OLED device architecture is with embodiment 4.
The device performance index is as follows:
Tristimulus coordinates: (0.42,0.42);
Play bright voltage: 3.5V;
High-high brightness: 18400cd/m2 (12V);
Luminous efficiency: 17.1cd/A.
The first step: get mol ratio and be 1: 2 1-methyl isophthalic acid, 4-phenyl-7-diethylamino quinoline-2 (1H)-ketone, the N-bromo-succinimide is a raw material, above-mentioned raw materials is dissolved in trichloromethane, and stirring at room 10 hours adds elutriation and goes out a large amount of solids, the washing solid, drying promptly gets corresponding bromo-derivative, productive rate 80%.
Second step: under nitrogen protection; product and phenylo boric acid (mol ratio is 1: 2) that the first step is obtained drop in the two-mouth bottle; four (triphenyl) phosphine palladium that adds catalytic amount) and mixed solvent (solution of potassium carbonate: toluene: methyl alcohol=1: 4: 4); keep 90-100 ℃ of temperature; stirred 24 hours, extracted with diethyl ether, (elutriant is petrol ether/ethyl acetate=3/1 to product through column chromatography; collection Rf=0.7 component) obtains high purity target product (Q7), productive rate about 50%.
The structural identification data:
MS：444.2219
The OLED device preparation of compound Q 7
Have the compound of structural formula Q1 except the compound with above-mentioned structural formula Q7 substitutes, prepared OLED device architecture is with embodiment 1.
The device performance index is as follows:
Tristimulus coordinates: (0.41,0.43);
Play bright voltage: 3.6V;
High-high brightness: 17000cd/m2 (12V);
Luminous efficiency: 13.9cd/A.
Claims (10)
1. general structure compound shown by formula I:
Formula I
Wherein,
R
1, R
2, R
3Identical or different, independently representative: hydrogen, fluorine, alkyl, cycloalkyl, substituted alkyl, aralkyl, aryl, heteroaryl, O-alkyl, O-substituted alkyl, O-aryl, O-heteroaryl, N-alkyl, N-substituted aryl, N-aryl, N-heteroaryl, aryl alkenyl or aromatic yl polysulfide yl;
A is an organic group;
M=0 or 1, when m=0, n=1 or 2, when m=1, n gets the integer more than or equal to 2;
P is 0 or smaller or equal to 2 positive integer, and k gets 0 or smaller or equal to 4 positive integer.
2. compound according to claim 1 is characterized in that:
Described R
1, R
2, R
3In alkyl be the alkyl of carbonatoms 1 to 20;
Described R
1, R
2, R
3In cycloalkyl be the cycloalkyl of carbonatoms 3 to 20;
Described R
1, R
2, R
3In substituted alkyl be the alkyl of the alkyl of the alkyl of the alkyl of 1 to 20 carbon atom replacing of halogen, 1 to 20 carbon atom that hydroxyl replaces, 1 to 20 carbon atom that cyano group replaces, 1 to 20 carbon atom that nitro replaces or the alkyl of amino 1 to 20 carbon atom that replaces;
Described R
1, R
2, R
3In aralkyl be the alkyl of 1 to 20 carbon atom replacing of aryl;
Described R
1, R
2, R
3In aryl be the aryl of 6 to 60 ring carbon atoms;
Described R
1, R
2, R
3In heteroaryl be the aromatic heterocyclic group of 5 to 50 annular atomses;
Described R
1, R
2, R
3In aryl alkenyl be the thiazolinyl of 2 to 20 carbon atoms replacing of aryl, the thiazolinyl of 2 to 20 carbon atoms that heteroaryl replaces;
Described R
1, R
2, R
3In aromatic yl polysulfide yl be the alkynyl of 2 to 20 carbon atoms replacing of aryl, the alkynyl of 2 to 20 carbon atoms that heteroaryl replaces.
3. compound according to claim 2 is characterized in that:
Described R
1, R
2, R
3In the alkyl of carbonatoms 1 to 20 be methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl;
Described R
1, R
2, R
3In the substituted alkyl with 1 to 20 carbon atom be methylol, the 1-hydroxyethyl, the 2-hydroxyethyl, 2-hydroxyl isobutyl-, 1, the 2-dihydroxy ethyl, 1,3-dihydroxyl sec.-propyl, 2, the 3 one dihydroxyl-tertiary butyl, 1,2,3 one trihydroxy-propyl group, methyl fluoride, the 1-fluoro ethyl, the 2-fluoro ethyl, 2-fluorine isobutyl-, 1,2-two fluoro ethyls, 1,3-difluoro sec.-propyl, 2, the 3-two fluoro-tertiary butyls, 1,2, the 3-trifluoro propyl, chloromethyl, the 1-chloroethyl, the 2-chloroethyl, 2-chlorine isobutyl-, 1, the 2-Dichloroethyl, 1,3-two chloro isopropyls, 2, the 3-two chloro-tertiary butyls, 1,2,3-three chloropropyls, brooethyl, the 1-bromotrifluoromethane, the 2-bromotrifluoromethane, 2-bromine isobutyl-, 1,2-two bromotrifluoromethanes, 1,3-dibromo sec.-propyl, 2, the 3-two bromo-tertiary butyls, 1,2,3-three bromopropyls, iodomethyl, 1-iodine ethyl, 2-iodine ethyl, 2-iodine isobutyl-, 1,2-diiodo-ethyl, 1,3-diiodo-sec.-propyl, 2, the 3-two iodo-tertiary butyls, 1,2,3-triiodo propyl group, amino methyl, the 1-amino-ethyl, the 2-amino-ethyl, 2-aminoisobutyric base, 1, the 2-diamino ethyl, 1,3-diamino sec.-propyl, 2,3-diamino-tertiary butyl or 1,2,3-triamino propyl group; Cyano methyl, 1-cyano ethyl, 2-cyano ethyl, 2-cyano group isobutyl-, 1,2-dicyano ethyl, 1,3-dicyano sec.-propyl, 2,3-dicyano-tertiary butyl, 1,2,3-tricyano propyl group, nitro methyl, 1-nitro-ethyl, 2-nitro-ethyl, 2-nitro isobutyl-, 1,2-dinitrobenzene ethyl, 1,3-dinitrobenzene sec.-propyl, 2,3-dinitrobenzene-tertiary butyl or 1,2,3-trinitro-propyl group;
Described R
1, R
2, R
3In the cycloalkyl of carbonatoms 3 to 20 be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, adamantyl or norborneol alkyl;
Described R
1, R
2, R
3In the alkyl of 1 to 20 carbon atom replacing of aryl be benzyl, the 1-phenylethyl, the 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, to methyl-benzyl, between methyl-benzyl, adjacent methyl-benzyl, p-chlorobenzyl, the m-chloro benzyl, o-chlorobenzyl, to bromobenzyl, between bromobenzyl, adjacent bromobenzyl, to the iodine benzyl, between the iodine benzyl, adjacent iodine benzyl, PAB, between aminobenzyl, adjacent aminobenzyl, to nitrobenzyl, between nitrobenzyl, adjacent nitrobenzyl, to the cyano group benzyl, between the cyano group benzyl, o-cyanobenzyl, 1-chloro-2-propyloxy phenyl base or trityl;
Described R
1, R
2, R
3In the aryl of 6 to 60 of carbon atoms be phenyl, the 1-naphthyl, the 2-naphthyl, the 1-anthryl, the 2-anthryl, the 9-anthryl, the 1-phenanthryl, the 2-phenanthryl, the 3-phenanthryl, the 4-phenanthryl, the 9-phenanthryl, the 1-naphthacenyl, the 2-naphthacenyl, the 9-naphthacenyl, the 1-pyrenyl, the 2-pyrenyl, the 4-pyrenyl, the 2-xenyl, the 3-xenyl, the 4-xenyl, p-terphenyl-4-base, p-terphenyl-3-base, p-terphenyl-2-base, meta-terphenyl-4-base, meta-terphenyl-3-base, meta-terphenyl-2-base, o-tolyl, between tolyl, p-methylphenyl, to tert-butyl-phenyl, right-(2-phenyl propyl) phenyl, 3-methyl-2-naphthyl, 4-methyl isophthalic acid-naphthyl, 4-methyl isophthalic acid-naphthyl, 4 '-methyl biphenyl or 4 "-tertiary butyl-p-terphenyl-4-base;
Described R
1, R
2, R
3In the aromatic heterocyclic group of 5 to 50 annular atomses be the 2-pyrryl, the 3-pyrryl, pyridyl, the 2-pyridyl, the 3-pyridyl, the 4-pyridyl, the 2-indyl, the 3-indyl, the 4-indyl, the 5-indyl, the 6-indyl, the 7-indyl, the 1-pseudoindoyl, the 3-pseudoindoyl, the 4-pseudoindoyl, the 5-pseudoindoyl, the 6-pseudoindoyl, the 7-pseudoindoyl, the 2-furyl, the 3-furyl, the 2-benzofuryl, the 3-benzofuryl, the 4-benzofuryl, the 5-benzofuryl, the 6-benzofuryl, the 7-benzofuryl, the 1-isobenzofuran-base, the 3-isobenzofuran-base, the 4-isobenzofuran-base, the 5-isobenzofuran-base, the 6-isobenzofuran-base, the 7-isobenzofuran-base, the 2-quinolyl, the 3-quinolyl, the 4-quinolyl, the 5-quinolyl, the 6-quinolyl, the 7-quinolyl, the 8-quinolyl, the 1-isoquinolyl, the 3-isoquinolyl, the 4-isoquinolyl, the 5-isoquinolyl, the 6-isoquinolyl, the 7-isoquinolyl, the 8-isoquinolyl, the 2-quinoxalinyl, the 5-quinoxalinyl, the 6-quinoxalinyl, the 1-carbazyl, the 2-carbazyl, the 3-carbazyl, the 4-carbazyl, 2-(9H-carbazyl) phenyl, 3-(9H-carbazyl) phenyl, 4-(9H-carbazyl) phenyl, 2-triphen amido, 3-triphen amido, 4-triphen amido, the 1-phenanthridinyl, the 2-phenanthridinyl, the 3-phenanthridinyl, the 4-phenanthridinyl, the 6-phenanthridinyl, the 7-phenanthridinyl, the 8-phenanthridinyl, the 9-phenanthridinyl, the 10-phenanthridinyl, the 1-acridyl, the 2-acridyl, the 3-acridyl, the 4-acridyl, the 9-acridyl, 1, the 7-phenanthrene is coughed up beautiful jade-2-base, 1, the 7-phenanthrene is coughed up beautiful jade-3-base, 1, the 7-phenanthrene is coughed up beautiful jade-4-base, 1, the 7-phenanthrene is coughed up beautiful jade-5-base, 1, the 7-phenanthrene is coughed up beautiful jade-6-base, 1, the 7-phenanthrene is coughed up beautiful jade-8-base, 1, the 7-phenanthrene is coughed up beautiful jade-9-base, 1, the 7-phenanthrene is coughed up beautiful jade-10-base, 1, the 8-phenanthrene is coughed up beautiful jade-2-base, 1, the 8-phenanthrene is coughed up beautiful jade-3-base, 1, the 8-phenanthrene is coughed up beautiful jade-4-base, 1, the 8-phenanthrene is coughed up beautiful jade-5-base, 1, the 8-phenanthrene is coughed up beautiful jade-6-base, 1, the 8-phenanthrene is coughed up beautiful jade-7-base, 1, the 8-phenanthrene is coughed up beautiful jade-9-base, 1, the 8-phenanthrene is coughed up beautiful jade-10-base, 1, the 9-phenanthrene is coughed up beautiful jade-2-base, 1, the 9-phenanthrene is coughed up beautiful jade-3-base, 1, the 9-phenanthrene is coughed up beautiful jade-4-base, 1, the 9-phenanthrene is coughed up beautiful jade-5-base, 1, the 9-phenanthrene is coughed up beautiful jade-6-base, 1, the 9-phenanthrene is coughed up beautiful jade-7-base, 1, the 9-phenanthrene is coughed up beautiful jade-8-base, 1, the 9-phenanthrene is coughed up beautiful jade-10-base, 1, the 10-phenanthrene is coughed up beautiful jade-2-base, 1, the 10-phenanthrene is coughed up beautiful jade-3-base, 1, the 10-phenanthrene is coughed up beautiful jade-4-base, 1, the 10-phenanthrene is coughed up beautiful jade-5-base, 2, the 9-phenanthrene is coughed up beautiful jade-1-base, 2, the 9-phenanthrene is coughed up beautiful jade-3-base, 2, the 9-phenanthrene is coughed up beautiful jade-4-base, 2, the 9-phenanthrene is coughed up beautiful jade-5-base, 2, the 9-phenanthrene is coughed up beautiful jade-6-base, 2, the 9-phenanthrene is coughed up beautiful jade-7-base, 2, the 9-phenanthrene is coughed up beautiful jade 8-base, 2, the 9-phenanthrene is coughed up beautiful jade-10-base, 2, the 8-phenanthrene is coughed up beautiful jade-1-base, 2, the 8-phenanthrene is coughed up beautiful jade-3-base, 2, the 8-phenanthrene is coughed up beautiful jade-4-base, 2, the 8-phenanthrene is coughed up beautiful jade-5-base, 2, the 8-phenanthrene is coughed up beautiful jade-6-base, 2, the 8-phenanthrene is coughed up beautiful jade-7-base, 2, the 8-phenanthrene is coughed up beautiful jade-9-base, 2, the 8-phenanthrene is coughed up beautiful jade-10-base, 2, the 7-phenanthrene is coughed up beautiful jade-1-base, 2, the 7-phenanthrene is coughed up beautiful jade-3-base, 2, the 7-phenanthrene is coughed up beautiful jade-4-base, 2, the 7-phenanthrene is coughed up beautiful jade-5-base, 2, the 7-phenanthrene is coughed up beautiful jade-6-base, 2, the 7-phenanthrene is coughed up beautiful jade-8-base, 2, the 7-phenanthrene is coughed up beautiful jade-9-base, 2, the 7-phenanthrene is coughed up beautiful jade-10-base, the 1-phenazinyl, the 2-phenazinyl, the 1-phenothiazinyl, the 2-phenothiazinyl, the 3-phenothiazinyl, the 4-phenothiazinyl, the 1-phenoxazinyl, the 2-phenoxazinyl, the 3-phenoxazinyl, the 4-phenoxazinyl, the 2-oxazolyl, the 4-oxazolyl, the 5-oxazolyl, 2-oxadiazole base, 5-oxadiazole base, 3-furazan base, the 2-thienyl, the 3-thienyl, the 2-benzothienyl, the 3-benzothienyl, the 4-benzothienyl, the 5-benzothienyl, the 6-benzothienyl, the 7-benzothienyl, the 1-isobenzo-thienyl, the 3-isobenzo-thienyl, the 4-isobenzo-thienyl, the 5-isobenzo-thienyl, the 6-isobenzo-thienyl, the 7-isobenzo-thienyl, 2-methylpyrrole-1-base, 2-methylpyrrole-3-base, 2-methylpyrrole-4-base, 2-methylpyrrole-5-base, 3-methylpyrrole-1-base, 3-methylpyrrole-2-base, 3-methylpyrrole-4-base, 3-methylpyrrole-5-base, 2-tertiary butyl pyrroles-4-base, 3-(2-phenyl propyl) pyrroles-1-base, 2-methyl isophthalic acid-indyl, 4-methyl isophthalic acid-indyl, 2-methyl-3-indyl, 4-methyl-3-indyl, the 2-tertiary butyl-1-indyl, the 4-tertiary butyl-1-indyl, the 2-tertiary butyl-3-indyl or the 4-tertiary butyl-3-indyl.
4. according to arbitrary described compound among the claim 1-3, it is characterized in that: A described in the formula I is fragrant organic group, is preferably the phenyl ring group, carbazole group, anthryl group or fluorene group.
5. according to arbitrary described compound among the claim 1-4, it is characterized in that: described compound is following 1)-7) in any one:
6. prepare the method for general structure compound shown by formula I, comprise the steps:
1) compound shown in the formula II and N-bromo-succinimide are reacted in organic solvent, obtain the compound shown in the formula III;
2) under anaerobic and alkaline condition, compound shown in the formula III and organic boronic to be reacted in the solvent that contains the Pd catalyzer, reaction finishes the back and extracts with ether, obtains the compound shown in the formula I;
(formula II)
(formula III).
7. method according to claim 6 is characterized in that: be reflected at described in the step 1) under the whipped state and carry out, the temperature of reaction of described reaction is 0-25 ℃, and the reaction times is 5-15 hour;
Described organic solvent is selected from following at least a: methylene dichloride, trichloromethane, dimethyl sulfoxide (DMSO), N, dinethylformamide, 1,2-ethylene dichloride, methyl alcohol, ethanol, ether, acetonitrile, acetone, benzene and toluene;
In the described reaction of step 1), the mol ratio of compound shown in the formula II and N-bromo-succinimide is 1: 1-1: 2.
8. according to claim 6 or 7 described methods, it is characterized in that: step 2) described in be reflected under the reflux state and carry out, the temperature of reaction of described reaction is 80-110 ℃, preferred 90-100 ℃, the reaction times is 18-48 hour;
Step 2) in the described reaction, the mol ratio of compound shown in the formula III and organic boronic is 1: 2-2: 1;
Described organic boronic is fragrant organic boronic, as phenylo boric acid, 2-naphthalene boronic acids, 4-(9-carbazyl) phenylo boric acid;
Step 2) catalyzer of Pd described in is two (dibenzalacetone) palladium, two (triphenylphosphine) palladium chloride, and four (triphenyl) phosphine palladiums etc. are preferably four (triphenyl) phosphine palladium;
Step 2) solvent described in is selected from following at least a: methylene dichloride, trichloromethane, dimethyl sulfoxide (DMSO), N, dinethylformamide, 1,2-ethylene dichloride, ether, acetonitrile, acetone, benzene and toluene.
9. the application of arbitrary described compound in the preparation organic electroluminescence device among the claim 1-5.
10. application according to claim 9, it is characterized in that: described organic electroluminescence device comprises negative electrode, anode and organic thin film layer, at least comprise organic luminous layer in the organic thin film layer between negative electrode and anode, and described organic luminous layer comprises arbitrary described compound among the claim 1-5 at least; Described organic electroluminescence device can be used in organic transistor, organic integration circuit, organic solar batteries, organic laser, organic sensor or the organic electronic label.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260492A (en) * | 2010-08-11 | 2011-11-30 | 中国科学院理化技术研究所 | Use of quinolone derivatives as organic light emitting diode (OLED) emitting materials in organic electroluminescent device |
| CN102683617A (en) * | 2012-05-22 | 2012-09-19 | 太原理工大学 | Application of levofloxacin in organic electroluminescent device |
| CN102683616A (en) * | 2012-05-22 | 2012-09-19 | 太原理工大学 | Application of ciprofloxacin as luminescent material in organic electroluminescent device |
| CN103965103A (en) * | 2013-01-31 | 2014-08-06 | 海洋王照明科技股份有限公司 | Organic semiconductor material, preparation method and electroluminescent device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4748791B2 (en) * | 2003-02-24 | 2011-08-17 | 独立行政法人科学技術振興機構 | Fluorescent lanthanide complex |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260492A (en) * | 2010-08-11 | 2011-11-30 | 中国科学院理化技术研究所 | Use of quinolone derivatives as organic light emitting diode (OLED) emitting materials in organic electroluminescent device |
| CN102683617A (en) * | 2012-05-22 | 2012-09-19 | 太原理工大学 | Application of levofloxacin in organic electroluminescent device |
| CN102683616A (en) * | 2012-05-22 | 2012-09-19 | 太原理工大学 | Application of ciprofloxacin as luminescent material in organic electroluminescent device |
| CN103965103A (en) * | 2013-01-31 | 2014-08-06 | 海洋王照明科技股份有限公司 | Organic semiconductor material, preparation method and electroluminescent device |
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