CN103242369A - Aromatic five-membered heterocyclo-substituted quinoline iridium (III) complex as well as preparation method and application thereof - Google Patents
Aromatic five-membered heterocyclo-substituted quinoline iridium (III) complex as well as preparation method and application thereof Download PDFInfo
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Abstract
The present invention relates to a kind of fragrant five-ring heterocycles substd quinolines iridium (III) complexs indicated by following general structure, the complex is reacted by C^N bidentate ligand fragrance five-ring heterocycles substituted chinoline derivative with three hydrated iridium trichlorides, iridium (III) the chlorine bridge dimer for obtaining respective ligand, further reacts with acetylacetone,2,4-pentanedione and is prepared. Target iridium (III) complex produced by the present invention may be used as electroluminescent phosphorescence material and phosphorescence dopant material is applied in organic electroluminescence device, by the substituent group for introducing different push-and-pull electronics, the photochromic adjusting of phosphorescence for carrying out title complex, realizes the red emission of complex.
Description
Technical field
The present invention relates to a kind of fragrant five-membered ring substd quinolines iridium (III) title complex, the preparation method of this title complex and application.
Technical background
Since C. W. Tang in 1987 finds 8-hydroxyquinoline aluminum (Alq first
3) electroluminescent since, the photic and electroluminescent of organic compound has been subjected to people's extensive concern.These organic light emission compounds are widely used in fields such as Organic Light Emitting Diode (OLEDs), organic sensing and bio-imaging.According to quantum theory, common organic light emission is divided into fluorescence radiation and phosphorescence is luminous.But, for most pure organic molecule and light metal title complex, owing to long lifetime and the spin of its triplet state are prohibited, thereby show nonradiative transition, so can only utilize its singlet, greatly reduced the luminous quantum efficiency of this type of material.And transition metal is because the heavy atoms effect of heavy atom, cause very strong spin-orbit coupling effect, make singlet obviously strengthen to the intersystem crossing of triplet state, thereby the luminous quantum efficiency of phosphor material obviously improves, namely utilize transition metal can take full advantage of the form of energy of singlet and triplet state as electroluminescent material, increase substantially luminous efficiency, can make luminous quantum efficiency reach 100% in theory.
Transition metal complex as luminescent material mainly contains iridium (III), platinum (II), osmium (II), rhenium (I), copper heavy metal complexes such as (I) at present, wherein because iridium (III) is the hexa-coordinate ion, the title complex that forms is approximate globular molecule, can effectively reduce the strong phosphorescence quenching effect between the complex of iridium molecule, thereby iridium (III) title complex has obtained using widely.
The glow color of iridium (III) title complex depends on the structure of part consumingly, so can select suitable part, and carry out chemically modified by atom or the functional group that it is introduced different electronegativity and volume, with the frontier molecular orbitals of adjusting complex of iridium molecule, thus the phosphorescent emissions of realization from gold-tinted to orange red smooth complex of iridium.
Summary of the invention
The purpose of this invention is to provide a kind of fragrant five-membered ring substd quinolines iridium (III) title complex, and the preparation method of this title complex and as the application of phosphorescent light-emitting materials.
Fragrant five-membered ring substd quinolines iridium provided by the invention (III) title complex is the title complex by following general formula (I) expression:
Wherein, R
1, R
2, R
3, R
4, R
5Representative independently of one another: hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group, C
1-4Fluoro-alkyl, C
1-4Fluoroalkyl, itrile group, phenyl, amino, hexichol amido, dimethylin, diethylin, piperidines-1-base; X represents sulphur or oxygen.
Further, each substituting group can be expressed as respectively in fragrant five-membered ring substd quinolines iridium provided by the invention (III) the title complex general formula (I):
R
1, R
2Represent hydrogen, R
3, R
4, R
5Representative independently of one another: hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group, C
1-4Fluoro-alkyl, C
1-4Fluoroalkyl, itrile group, phenyl, amino, hexichol amido, dimethylin, diethylin, piperidines-1-base; X represents sulphur or oxygen;
Perhaps, R
1Represent hydrogen, halogen, itrile group, R
2, R
3Represent hydrogen, R
4, R
5Representative independently of one another: hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group, C
1-4Fluoro-alkyl, C
1-4Fluoroalkyl, itrile group, phenyl, amino, hexichol amido, dimethylin, diethylin, piperidines-1-base; X represents sulphur or oxygen;
Perhaps, R
1Represent hydrogen, R
2, R
3, R
4, R
5Representative independently of one another: hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group, C
1-4Fluoro-alkyl, C
1-4Fluoroalkyl, itrile group, phenyl, amino, hexichol amido, dimethylin, diethylin, piperidines-1-base; X represents sulphur or oxygen;
Perhaps, R
1Represent hydrogen, halogen, itrile group, R
3Represent hydrogen, R
2, R
4, R
5Representative independently of one another: hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group, C
1-4Fluoro-alkyl, C
1-4Fluoroalkyl, itrile group, phenyl, amino, hexichol amido, dimethylin, diethylin, piperidines-1-base; X represents sulphur or oxygen.
The present invention provides the preparation method of described fragrant five-membered ring substd quinolines iridium (III) title complex simultaneously, be by
C^NBidentate ligand fragrance five-membered ring substituted chinoline derivative and the reaction of three hydration iridous chlorides behind iridium (III) the chlorine bridge dimer of acquisition respective ligand, further obtain with the methyl ethyl diketone prepared in reaction.
Particularly, be under protection of inert gas, in the alkoxyethanol solvent system, by the fragrant five-membered ring substituted chinoline derivative part and the mol ratio of three hydration iridous chlorides according to 2-2.5:1 of general formula (II) expression, in iridium (III) the chlorine bridge dimer of 90-110 ℃ of back flow reaction acquisition respective ligand; Under protection of inert gas; in the alkoxyethanol solvent system; catalyzer anhydrous alkali metal carbonate exists down; according to the mol ratio of 1:2-2.5, obtain fragrant five-membered ring substd quinolines iridium (III) title complex in 80-110 ℃ of reaction by iridium (III) the chlorine bridge dimer of respective ligand and methyl ethyl diketone.
Wherein, R
1, R
2, R
3, R
4, R
5Representative independently of one another: hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group, C
1-4Fluoro-alkyl, C
1-4Fluoroalkyl, itrile group, phenyl, amino, hexichol amido, dimethylin, diethylin, piperidines-1-base; X represents sulphur or oxygen.
Further, each substituting group can be expressed as respectively in the fragrant five-membered ring substituted chinoline derivative part of above-mentioned general formula (II) expression:
R
1, R
2Represent hydrogen, R
3, R
4, R
5Representative independently of one another: hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group, C
1-4Fluoro-alkyl, C
1-4Fluoroalkyl, itrile group, phenyl, amino, hexichol amido, dimethylin, diethylin, piperidines-1-base; X represents sulphur or oxygen;
Perhaps, R
1Represent hydrogen, halogen, itrile group, R
2, R
3Represent hydrogen, R
4, R
5Representative independently of one another: hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group, C
1-4Fluoro-alkyl, C
1-4Fluoroalkyl, itrile group, phenyl, amino, hexichol amido, dimethylin, diethylin, piperidines-1-base; X represents sulphur or oxygen;
Perhaps, R
1Represent hydrogen, R
2, R
3, R
4, R
5Representative independently of one another: hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group, C
1-4Fluoro-alkyl, C
1-4Fluoroalkyl, itrile group, phenyl, amino, hexichol amido, dimethylin, diethylin, piperidines-1-base; X represents sulphur or oxygen;
Perhaps, R
1Represent hydrogen, halogen, itrile group, R
3Represent hydrogen, R
2, R
4, R
5Representative independently of one another: hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group, C
1-4Fluoro-alkyl, C
1-4Fluoroalkyl, itrile group, phenyl, amino, hexichol amido, dimethylin, diethylin, piperidines-1-base; X represents sulphur or oxygen.
Among the above-mentioned preparation method, employed anhydrous alkali metal carbonate is Carbon Dioxide lithium, anhydrous sodium carbonate, Anhydrous potassium carbonate, Carbon Dioxide rubidium or Carbon Dioxide caesium, and it uses molar weight to be 5-10 times of the methyl ethyl diketone molar weight.
Wherein, the alkoxyethanol solvent system is specially the mixed solvent that 2-methyl cellosolve or cellosolvo and water are formed, and wherein the volume ratio of alkoxyethanol and water is 3:1.
Fragrant five-membered ring substd quinolines iridium (III) title complex that the present invention prepares can be used as the organic electroluminescent phosphor material, and perhaps the phosphorescence dopant material of organic electrophosphorescenpolymer material of main part is applied in the organic electroluminescence device.
In organic electroluminescence device, use title complex of the present invention, by introducing the substituting group of different push-and-pull electronics, can carry out the photochromic adjusting of phosphorescence of target title complex, realize the red emission of title complex.
And then, the present invention also comprises a kind of organic electroluminescence device, described organic luminescent device has first electrode, second electrode, and one or more layers organic function layer that between first electrode and second electrode, forms, wherein include fragrant five-membered ring substd quinolines iridium of the present invention (III) title complex in one deck organic function layer at least.
Preferably, fragrant five-membered ring substd quinolines iridium (III) title complex as the dopant material of phosphorescent light body material, constitutes the luminescent layer of organic electroluminescence devices with phosphorescent light body material jointly in organic electroluminescence device.Wherein, the weight ratio of fragrant five-membered ring substd quinolines iridium (III) title complex and phosphorescent light body material is 1-9:100.
Described luminescent layer can adopt the vacuum vapour deposition preparation.Concrete technology be with iridium (III) title complex and small molecules material of main part while evaporation under vacuum condition, by two independently quartz resonator control separately vaporator rate, thereby control both content.Small molecules as material of main part comprises 4,4 '-
N, N'-two carbazole biphenyl (CBP), 2-(4-phenylbenzene)-5-(4-tert-butyl-phenyl)-1,3,4-oxadiazole (PBD), 1,3,5-three (2-
N-phenyl benzimidazolyl-) benzene (TPBI), 3-(4-phenylbenzene)-5-(4-tert-butyl-phenyl)-4-(4-ethylphenyl)-, 1,2,4-triazole (TAZ) etc.Between anode ITO and luminescent layer, introduce hole transmission layer by vacuum vapour deposition simultaneously, between metallic cathode and luminescent layer, introduce one to two layer of organic molecule layer with hole barrier or electric transmission function, with the structure multilayer device.
The luminescent layer of organic electroluminescence device also can adopt the preparation of solution spin-coating method.Concrete technology be with iridium (III) title complex and the blend of polymer main body material, is dissolved in the chloroform, is spin-coated on through polythiofuran derivative (PEDOT) modification or without the ito glass surface of its modification, is prepared into luminescent layer.The derivative that comprises polystyrene support, polyhenylene, Polyvinyl carbazole, polycarbazole, poly-fluorenes or poly-fluorenes as the polymer of material of main part.In addition, in luminescent layer, can also further mix small molecules carrier transmission material such as 2-(4-phenylbenzene)-5-(4-tert-butyl-phenyl)-1,3,4-oxadiazole (PBD), 1,3,5-three (2-
N-phenyl benzimidazolyl-) benzene (TPBI), 3-(4-phenylbenzene)-5-(4-tert-butyl-phenyl)-4-(4-ethylphenyl)-, 1,2,4-triazole (TAZ),
N,
N'-two (3-aminomethyl phenyl)-
N,
N'-phenylbenzene-1,1 '-phenylbenzene-4,4 '-diamines (TPD) or
N, N'-two (1-naphthyl)-
N, N'-phenylbenzene-1,1 '-phenylbenzene-4,4 '-diamines (NPB) etc.Load onto in set of devices, behind the intact luminescent layer of spin coating directly the evaporation metal electrode make single layer device, also can vacuum vapour deposition between metal electrode and luminescent layer, further introduce one and construct multilayer device to two-layer organic molecule layer with hole barrier or electric transmission function.
Description of drawings
Fig. 1 is embodiment 1 title complex [2 (Thip-2-Ph) 4Me]
2The proton nmr spectra of Ir (acac).
Fig. 2 is embodiment 1 title complex [2 (Thip-2-Ph) 4Me]
2The carbon-13 nmr spectra of Ir (acac).
Fig. 3 is embodiment 1 title complex [2 (Thip-2-Ph) 4Me]
2The hot ellipsoid figure of the X ray single crystal diffraction of Ir (acac).
Fig. 4 is embodiment 1 title complex [2 (Thip-2-Ph) 4Me]
2Ir (acac) is at methylene dichloride medium ultraviolet visible absorption spectra, photoluminescence spectra and electroluminescent spectrum.
Fig. 5 is the electroluminescent spectrum of organic electroluminescence device under different voltages that application examples 1 is made.
Fig. 6 is that the brightness of the organic electroluminescence device made of application examples 1 and current density are with the change curve of voltage.
Fig. 7 is that the current efficiency of the organic electroluminescence device made of application examples 1 and luminous efficiency are along with the change curve under the current density.
Embodiment
Further describe the present invention below in conjunction with specific embodiment, but following embodiment is not for restriction practical range of the present invention, every equivalence of doing according to the technology of the present invention content changes and retouching, all should be included within the technology category of the present invention.
Embodiment 1: title complex [2 (Thip-2-Ph) 4Me]
2Ir's (acac) is synthetic
(1) 4-toluquinoline-2 (1
HSynthesizing of)-ketone
The adding of the 40mL vitriol oil is had in the there-necked flask of stirrer, add acetoacetanilide 17.7g under the normal temperature gradually, add the 10mL vitriol oil after adding again, be warming up to 80 ℃ of reaction 10min, carefully pour in the 400mL frozen water, separate out a large amount of white precipitates, the decompress filter after washing is to neutral, and 30 ℃ of vacuum-dryings get 4-toluquinoline-2 (1
H)-ketone white solid, ethyl alcohol recrystallization is separated out colourless rhabdolith, productive rate 87%.
1H?NMR?(600MHz,?CDCl
3)?δ(ppm):?11.95(br;?1H);?7.70(dd;?
J=1.20Hz;?
J=7.20Hz;?1H);?7.52(dt;?
J=1.20Hz;?
J=7.20Hz;?1H);?7.42(dd;?
J=1.20Hz;?
J=7.20Hz;?1H);?7.26(dt;?
J=1.20Hz;?
J=7.20Hz;?1H);?6.61(q;?
J=1.20Hz;?1H);?2.53(d;?
J=1.20Hz;?3H)。
(2) 2-chloro-4-toluquinoline is synthetic
Get 4-toluquinoline-2 (1
H)-ketone 5.0g, phosphorus oxychloride 40mL.Phosphorus oxychloride is positioned in the there-necked flask that has stirrer, slowly adds 4-toluquinoline-2 (1
H)-ketone powder, the temperature that slowly raises is to refluxing stirring reaction 20min, stopped reaction, vacuum rotary steam are removed most of solvent phosphorus oxychloride, and residuum is poured in the frozen water, be adjusted to neutrality with aqueous sodium hydroxide solution, there is precipitation to separate out, uses extracted with diethyl ether three times, wash ether again three times mutually, anhydrous magnesium sulfate drying, placement volatilizes naturally, separates out 2-chloro-4-toluquinoline colourless acicular crystal, productive rate 94%.
1H?NMR?(600MHz,?CDCl
3)?δ(ppm):?8.02(dd;?
J=1.20Hz;?
J=8.40Hz;?1H);?7.97(dd;?
J=1.20Hz;?
J=8.40Hz;?1H);?7.73(ddd;?
J=1.20Hz;?
J=7.20Hz;?
J=8.40Hz;?1H);?7.58(ddd;?
J=1.20Hz;?
J=6.60Hz;?
J=8.40Hz;?1H);?7.26(q;?
J=0.60Hz;?1H);?2.70(d;?
J=0.60Hz;?3H)。
(3) 2-(thiophene-2-yl)-4-toluquinoline is synthetic
Get 2-chloro-4-toluquinoline 3.0g, thiophene-2-boric acid 2.163g, Pd (PPh
3)
4640mg, the 20mL saturated aqueous sodium carbonate, the 10mL anhydrous methanol, toluene 40mL, add successively in the there-necked flask of band stirrer, logical nitrogen is behind the back flow reaction 22h, discard water layer earlier, use the aqueous sulfuric acid extracting toluene layer of proper concn then, have a large amount of yellow mercury oxides to generate, repeatedly extraction fully merges acidic precipitation in the back, precipitate with the capacity deionized water dissolving, obtain faint yellow acidic aqueous solution, remove by filter a small amount of insolubles, get faint yellow clear aqueous solution, with the potassium hydroxide solution adjustment of acidity water of proper concn to weakly alkaline, separate out a large amount of white solids, ethyl acetate extraction obtains the yellow solid head product, obtain colourless rhomboidan 3.25g, productive rate 85.4% through the sherwood oil recrystallization.
1H?NMR?(600MHz,?DMSO-d
6)?δ(ppm):?8.05(dd;?
J=0.60Hz;?
J=7.20Hz;?1H);?8.01(s;?1H);?7.98(dd;?
J=0.60Hz;?
J=3.60Hz;?1H);?7.95(d;?
J=8.40Hz;?1H);?7.74(ddd;?
J=1.20Hz;?
J=7.20Hz;?
J=8.40Hz;?1H);?7.72(dd;?
J=1.20Hz;?
J=3.60Hz;?1H);?7.58(ddd;?
J=1.20Hz;?
J=7.20Hz;?
J=8.40Hz;?1H);?7.22(dd;?
J=3.60Hz;?
J=4.80Hz;?1H);?2.73(s;?3H)。
(4) chlorine bridging Cyclometalated iridium (III) is dimeric synthetic
Get 2-(thiophene-2-yl)-4-toluquinoline 0.676g, three hydration iridous chloride 0.53g, cellosolvo 12mL, deionized water 4mL adds in two mouthfuls of flasks of band stirrer logical nitrogen successively, be heated to 110 ℃ of backflow stirring reaction 24h, reaction naturally cools to room temperature after finishing, and pours the 40mL deionized water in reaction solution, separate out the cotton-shaped solid of a large amount of intense violet colors, filter, washing, chloroform washs back 45 ℃ of vacuum-dryings and gets the intense violet color solid.
(5) title complex [2 (Thip-2-Ph) 4Me]
2Ir's (acac) is synthetic
Get 2-(thiophene-2-yl)-4-toluquinoline and close iridium (III) chlorine bridge dimer 0.509g, methyl ethyl diketone 94.2mg, anhydrous sodium carbonate 319mg, cellosolvo 15mL, add successively in two mouthfuls of flasks of band stirrer, logical nitrogen refluxes and stirs 24h, use the methylene dichloride dilute reaction solution, filter orange red methylene dichloride clear liquor, fully cellosolvo, dried over anhydrous sodium carbonate are removed in washing, leave standstill and volatilize solvent, separate out title complex [2 (Thip-2-Ph) 4Me]
2Ir (acac) scarlet crystal.
Proton nmr spectra is as shown in Figure 1:
1H NMR (600MHz, CDCl
3, 298 K) and δ (ppm): 8.39-8.37 (m; 2H); 7.90-7.87 (m; 2H); 7.57 (s; 2H); 7.45 (d;
J=3.60Hz; 2H); 7.44 (d;
J=3.00Hz; 2H); 7.09 (d;
J=4.20 Hz; 2H); 6.24 (d;
J=4.80 Hz; 2H); 4.83 (s; 1H); 2.88 (s; 6H); 1.62 (s; 6H).δ=4.83ppm, 1.62ppm are respectively the chemical shift of the two key hydrogen of assistant ligand methyl ethyl diketone in the complex molecule and methyl hydrogen; δ=2.88ppm is the chemical shift of methyl hydrogen on the cyclic metal complexes.
Carbon-13 nmr spectra as shown in Figure 2,
13C{
1H} NMR (150MHz, CDCl
3, 298 K) and δ (ppm): 185.51,166.36,153.04,149.89,146.32,139.72,134.34,130.26,128.54,125.85,125.61,124.44,123.83,117.51,100.71,28.25,18.94.δ=100.71ppm, 28.25ppm are respectively the chemical shift of assistant ligand methyl ethyl diketone double key carbon and methyl carbon in the complex molecule; δ=18.94ppm is the chemical shift of methyl carbon on the cyclic metal complexes.
Title complex [2 (Thip-2-Ph) 4Me]
2The monocrystalline of Ir (acac) is separated out from methylene dichloride.Be under 298 (2) the K conditions in temperature, choose [2 (Thip-2-Ph) 4Me]
2Ir (acac) single crystal is with German Bruker Smart CCD single crystal diffractometer Mo
K α(λ=0.71073) collects diffraction data; SHELXTL software is adopted in the parsing of single crystal structure.
Single crystal structure as shown in Figure 3.Title complex [2 (Thip-2-Ph) 4Me]
2Ir (acac) molecular structure has
C 2Symmetry, oblique system, the P21/n spacer, crystal data and acquisition of information are as follows.
Bond distance, the bond angle of the chemical bond that forms with metal iridium (III) coordination in the molecule are as shown in the table.
Fig. 4 uses Hitachi Model F-7000 FL spectrograph, the title complex that records [2 (Thip-2-Ph) 4Me] for being solvent with the methylene dichloride under 298K
2The fluorescence spectrum figure of Ir (acac), wherein glow peak is positioned at the 615nm place, belongs to red emission.
Embodiment 2: title complex [2 (Thip-2-Ph) 3F4Me]
2Ir's (acac) is synthetic
(1) 3-bromo-4-toluquinoline-2 (1
HSynthesizing of)-ketone
Get the 4-toluquinoline-2 (1 that embodiment 1 synthesizes
H)-ketone 7.0g, bromine 7.04g, anhydrous acetic acid 100mL, dry DMF 45mL.To be dissolved with 4-toluquinoline-2 (1 earlier
HThe anhydrous acetic acid solution of)-ketone adds in the there-necked flask of band stirrer, lucifuge is heated to 65 ℃ of stirrings, drip the anhydrous acetic acid solution of bromine fast, dropwise, add the 45mL dry DMF, reaction solution becomes brown transparent liquid, behind 65 ℃ of following stirring reaction 5h, reaction solution becomes faint yellow transparence, stop heating, slowly a large amount of white crystals are separated out in cooling, and reaction product is poured in the 600mL water, separate out the cotton-shaped solid of a large amount of whites, suction filtration gets white filter cake, washes three times, obtains the cotton shape white powder after 60 ℃ of vacuum-dryings, heavy 8.93g, productive rate 85%.
1H?NMR?(600MHz,?DMSO-d
6)?δ(ppm):?12.13(brs;?1H);?7.83(dd;?
J=1.20Hz;?
J=8.40Hz;?1H);?7.55(ddd;?
J=1.20Hz;?
J=7.20Hz;?
J=8.40Hz;?1H);?7.35(dd;?
J=1.20Hz;?
J=8.40Hz;?1H);?7.24(ddd;?
J=1.20Hz;?
J=7.20Hz;?
J=8.40Hz;?1H);?2.64(s;?3H)。
(2) 3-fluoro-4-toluquinoline-2 (1
HSynthesizing of)-ketone
Get 3-bromo-4-toluquinoline-2 (1
H)-ketone 2.37g; anhydrous potassium fluoride 2.32g; 18-is preced with-6 264mg, and anhydrous DMSO 40mL adds in the there-necked flask of band stirrer simultaneously; nitrogen protection is reacted 24h down for following 120 ℃; pour into after reaction finishes and separate out white flocks in the big water gaging, suction filtration is fully washed back 50 ℃ of following vacuum-dryings; get clear crystal with ethyl alcohol recrystallization then, productive rate 50%.
1H?NMR?(600MHz,?DMSO-d
6)?δ(ppm):?12.15(brs;?1H);?7.70(d;?
J=7.20Hz;?1H);?7.46(d;?
J=7.20Hz;?1H);?7.32(dd;?
J=7.80Hz;?1H);?7.25(d;?
J=7.20Hz;?1H);?2.35(s;?3H)。
(3) 2-chloro-3-fluoro-4-toluquinoline is synthetic
Get 3-fluoro-4-toluquinoline-2 (1
H)-ketone 5.0g, phosphorus oxychloride 40mL.The preparation method is with embodiment 1 step (2).
(4) 2-(thiophene-2-yl)-3-fluoro-4-toluquinoline is synthetic
Get 2-chloro-3-fluoro-4-toluquinoline 3.0g, thiophene-2-boric acid 2.163g, Pd (PPh
3)
4640mg, 20mL saturated aqueous sodium carbonate, 10mL anhydrous methanol, toluene 40mL.The preparation method is with embodiment 1 step (3).
(5) chlorine bridging Cyclometalated iridium (III) is dimeric synthetic
Get 2-(thiophene-2-yl)-3-fluoro-4-toluquinoline 0.676g, three hydration iridous chloride 0.53g, cellosolvo 12mL, deionized water 4mL.The preparation method is with embodiment 1 step (4).
(6) title complex [2 (Thip-2-Ph) 3F4Me] 2Iracac's is synthetic
Get 2-(thiophene-2-yl)-3-fluoro-4-toluquinoline and close iridium (III) chlorine bridge dimer 0.509g, methyl ethyl diketone 94.2mg, anhydrous sodium carbonate 319mg, cellosolvo 15mL.The preparation method is with embodiment 1 step (5).
Embodiment 3: title complex [2 (Thip-2-Ph) 3,7DiF4Me]
2Ir's (acac) is synthetic
(1) 3,7-two bromo-4-toluquinolines-2 (1
HSynthesizing of)-ketone
Get the 4-toluquinoline-2 (1 that embodiment 1 synthesizes
H)-ketone 7.0g, bromine 14.07g, anhydrous acetic acid 100mL, dry DMF 45mL.To be dissolved with 4-toluquinoline-2 (1
HThe anhydrous acetic acid solution of)-ketone adds in the there-necked flask of band stirrer, lucifuge is heated to 65 ℃ of stirrings, drip the anhydrous acetic acid solution of bromine fast, after dropwising, add the 45mL dry DMF again, reaction solution becomes brown transparent liquid, 65 ℃ of following stirring reaction 10h, reaction solution becomes faint yellow transparence, stop heating, slowly cooling has a large amount of white crystals to separate out, reaction product is poured in the 600mL water, separate out the cotton-shaped solid of a large amount of whites, suction filtration gets white filter cake, washes three times, 60 ℃ of vacuum-dryings obtain the cotton shape white powder, productive rate 70%.
1H?NMR?(600MHz,?DMSO-d
6)?δ(ppm):?11.69(brs;?1H);?7.96(d;?
J=1.80Hz;?1H);?7.70(dd;?
J=1.80Hz;?
J=9.00Hz;?1H);?7.28(d;?
J=9.00Hz;?1H);?2.62(s;?3H)。
(2) 3,7-two fluoro-4-toluquinolines-2 (1
HSynthesizing of)-ketone
Get 3,7-, two bromo-4-toluquinolines-2 (1
H)-ketone 2.37g, anhydrous potassium fluoride 2.32g, 18-is preced with-6 264mg, anhydrous DMSO 40mL.The preparation method is with embodiment 2 steps (2).
(3) the 2-chloro-3,7-two fluoro-4-toluquinolines synthetic
Get 3,7-, two fluoro-4-toluquinolines-2 (1
H)-ketone 5.0g, phosphorus oxychloride 40mL.The preparation method is with embodiment 1 step (2).
(4) 2-(thiophene-2-yl)-3,7-two fluoro-4-toluquinolines synthetic
Get 2-chloro-3,7-two fluoro-4-toluquinoline 3.0g, thiophene-2-boric acid 2.163g, Pd (PPh
3)
4640mg, 20mL saturated aqueous sodium carbonate, 10mL anhydrous methanol, toluene 40mL.The preparation method is with embodiment 1 step (3).
(5) chlorine bridging Cyclometalated iridium (III) is dimeric synthetic
Get 2-(thiophene-2-yl)-3,7-two fluoro-4-toluquinoline 0.676g, three hydration iridous chloride 0.53g, cellosolvo 12mL, deionized water 4mL.The preparation method is with embodiment 1 step (4).
(6) title complex [2 (Thip-2-Ph) 3,7DiF4Me]
2Ir's (acac) is synthetic
Get 2-(thiophene-2-yl)-3,7-two fluoro-4-toluquinolines close iridium (III) chlorine bridge dimer 0.509g, methyl ethyl diketone 94.2mg, anhydrous sodium carbonate 319mg, cellosolvo 15mL.The preparation method is with embodiment 1 step (5).
Embodiment 4: title complex [2 (Thip-2-Ph) 4FMe]
2Ir's (acac) is synthetic
(1)
NSynthesizing of-ω-bromo alpha.-acetylacetanilide
Get
N-bromo alpha.-acetylacetanilide 25g, bromine 18.06g, chloroform 150mL.To be dissolved with 25g
NThe chloroformic solution of-bromo alpha.-acetylacetanilide adds in the there-necked flask of band stirrer, dropwise splash into the chloroformic solution of bromine under 30 ℃, about 1.5h drips off, reaction solution becomes the sundown transparent liquid, slowly be warmed up to 50 ℃ and stir 2h, reaction finishes the back and becomes the white opacity shape, suitably after the cooling, suction filtration gets white filter cake, use twice of a small amount of methylene dichloride and absolute ethanol washing filter cake more respectively, solution washing filter cake with S-WAT and yellow soda ash is extremely neutral, and suction filtration gets white filter cake, and 50 ℃ of vacuum-dryings get white powder.
(2) 4-bromomethyl quinoline-2 (1
HSynthesizing of)-ketone
Get
N-
ω-alpha.-acetylacetanilide 20.0g, vitriol oil 40mL.The adding of the 40mL vitriol oil is had in the there-necked flask of stirrer, add gradually under the normal temperature
N-alpha.-acetylacetanilide 17.7g, be warming up to 80 ℃ the reaction 10min after, carefully pour in the 400mL frozen water, separate out a large amount of white precipitates, decompress filter is washed to neutrality.30 ℃ of vacuum-dryings get white solid, productive rate 80%.
1H?NMR?(600MHz,?DMSO-d
6)?δ(ppm):?11.80(brs;?1H);?7.84(dd;?
J=1.20Hz;?
J=7.80Hz;?1H);?7.53(ddd;?
J=1.20Hz;?
J=7.20Hz;?
J=8.40Hz;?1H);?7.35(dd;?
J=1.20Hz;?
J=8.40Hz;?1H);?7.25(ddd;?
J=1.20Hz;?
J=7.20Hz;?
J=8.40Hz;?1H);?6.74(s;1H);?4.90(s;?2H)。
(3) 4-methyl fluoride quinoline-2 (1
HSynthesizing of)-ketone
Get 4-bromomethyl quinoline-2 (1
H)-ketone 2.37g, anhydrous potassium fluoride 2.32g, 18-is preced with-6 264mg, anhydrous DMSO 40mL.The preparation method is with embodiment 2 steps (2).
(4) 2-chloro-4-methyl fluoride quinoline is synthetic
Get 4-methyl fluoride quinoline-2 (1
H)-ketone 5.0g, phosphorus oxychloride 40mL.The preparation method is with embodiment 1 step (2).
(5) 2-(thiophene-2-yl)-4-methyl fluoride quinoline is synthetic
Get 2-chloro-4-methyl fluoride quinoline 3.0g, thiophene-2-boric acid 2.163g, Pd (PPh
3)
4640mg, 20mL saturated aqueous sodium carbonate, 10mL anhydrous methanol, toluene 40mL.The preparation method is with embodiment 1 step (3).
(6) chlorine bridging Cyclometalated iridium (III) is dimeric synthetic
Get 2-(thiophene-2-yl)-4-methyl fluoride quinoline 0.676g, three hydration iridous chloride 0.53g, cellosolvo 12mL, deionized water 4mL.The preparation method is with embodiment 1 step (4).
(7) title complex [2 (Thip-2-Ph) 4FMe] 2Iracac's is synthetic
Get 2-(thiophene-2-yl)-4-methyl fluoride quinoline and close iridium (III) chlorine bridge dimer 0.509g, methyl ethyl diketone 94.2mg, anhydrous sodium carbonate 319mg, cellosolvo 15mL.The preparation method is with embodiment 1 step (5).
Embodiment 5: title complex [2 (Thip-2-Ph) 7F4FMe]
2Ir's (acac) is synthetic
(1) 4-brooethyl-7-bromoquinoline-2 (1
HSynthesizing of)-ketone
Get the 4-bromomethyl quinoline-2 (1 that embodiment 4 synthesizes
H)-ketone 2.0g, bromine 1.35g, anhydrous acetic acid 80mL, dry DMF 20mL.80mL is contained 4-bromomethyl quinoline-2 (1
HThe anhydrous acetic acid of)-ketone adds in the there-necked flask of stirrer, lucifuge is heated to 65 ℃, stir the DMF solution that drips bromine down fast, dropwise afterreaction liquid and be brown clear liquor, behind the reaction 24h, reaction solution is light golden yellow, pour into after the cooling in the 1200mL water, separate out the cotton-shaped solid of a large amount of whites, suction filtration and wash three times after, 50 ℃ of following vacuum-dryings.
1H?NMR(600MHz,?DMSO-d
6)?δ(ppm):?11.94(brs;?1H);?8.01(d;?
J=2.40Hz;?1H);?7.69(dd;?
J=2.40Hz;?
J=9.00Hz;?1H);?7.23(d;?
J=9.00Hz;?1H);?6.79(s;1H);?4.92(s;?2H)。
(2) 4-methyl fluoride-7-fluorine quinoline-2 (1
HSynthesizing of)-ketone
Get 4-brooethyl-7-bromoquinoline-2 (1
H)-ketone 2.37g, anhydrous potassium fluoride 4.64g, 18-is preced with-6 264mg, anhydrous DMSO 40mL.The preparation method is with embodiment 2 steps (2).
(5) 2-chloro-4-methyl fluoride-7-fluorine quinoline is synthetic
Get 4-methyl fluoride-7-fluorine quinoline-2 (1
H)-ketone 5.0g, phosphorus oxychloride 40mL.The preparation method is with embodiment 1 step (2).
(6) 2-(thiophene-2-yl)-4-methyl fluoride-7-fluorine quinoline is synthetic
Get 2-chloro-4-methyl fluoride-7-fluorine quinoline 3.0g, thiophene-2-boric acid 2.163g, Pd (PPh
3)
4640mg, 20mL saturated aqueous sodium carbonate, 10mL anhydrous methanol, toluene 40mL.The preparation method is with embodiment 1 step (3).
(7) chlorine bridging Cyclometalated iridium (III) is dimeric synthetic
Get 2-(thiophene-2-yl)-4-methyl fluoride-7-fluorine quinoline 0.676g, three hydration iridous chloride 0.53g, cellosolvo 12mL, deionized water 4mL.The preparation method is with embodiment 1 step (4).
(8) title complex [2 (Thip-2-Ph) 7F4FMe]
2Ir's (acac) is synthetic
Get 2-(thiophene-2-yl)-4-methyl fluoride-7-fluorine quinoline and close iridium (III) chlorine bridge dimer 0.509g, methyl ethyl diketone 94.2mg, anhydrous sodium carbonate 319mg, cellosolvo 15mL.The preparation method is with embodiment 1 step (5).
Application examples 1
Use embodiment 1 title complex [2 (Thip-2-Ph) 4Me]
2Ir (acac) is entrained in the CBP material of main part and makes organic electroluminescence device.At first, the surperficial evaporation 40nm's that is coated with ito glass
N,
N'-two (1-naphthyl)-
N,
N'-phenylbenzene-1,1 '-phenylbenzene-4,4 '-diamines (NPB) is as hole transmission layer.Then, dopant deposition has 6%[2 (4FPh) 4Me on hole transmission layer]
2The CBP of Ir (acac) forms the luminescent layer of 30nm, and is last, deposits hole blocking layer (BCP:10nm), electron transfer layer (Alq successively
3: 30nm), interfacial layer (LiF:1nm) and negative electrode (Al:150nm).
The electroluminescent spectrum of test component as shown in Figure 5, emission peak is positioned at 620nm, chromaticity coordinates CIE value X=0.64, Y=0.33.Current density-the voltage of device-brightness curve has rectification characteristic preferably as shown in Figure 6, and high-high brightness is 3460cd/m
2, current density is 100mA/cm
-2Following brightness 2334cd/m
-2, be 100cd/m in brightness
2And current density is 100mA/cm
2Under voltage be respectively 12.5V and 15.5V.Current efficiency-the current density of device-power efficiency as shown in Figure 7, fully-factored load current density 100mA/cm
2Under current efficiency be respectively 2.4cd/A and 2.2cd/A, fully-factored load current density 100mA/cm
2Under power efficiency be respectively 0.56lm/W, 0.45lm/W.
Claims (11)
1. a fragrant five-membered ring substd quinolines iridium (III) title complex is the title complex of following general formula (I) expression:
Wherein, R
1, R
2, R
3, R
4, R
5Representative independently of one another: hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group, C
1-4Fluoro-alkyl, C
1-4Fluoroalkyl, itrile group, phenyl, amino, hexichol amido, dimethylin, diethylin, piperidines-1-base; X represents sulphur or oxygen.
2. fragrant five-membered ring substd quinolines iridium according to claim 1 (III) title complex, wherein R
1, R
2Represent hydrogen, R
3, R
4, R
5Representative independently of one another: hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group, C
1-4Fluoro-alkyl, C
1-4Fluoroalkyl, itrile group, phenyl, amino, hexichol amido, dimethylin, diethylin, piperidines-1-base; X represents sulphur or oxygen.
3. fragrant five-membered ring substd quinolines iridium according to claim 1 (III) title complex, wherein R
1Represent hydrogen, halogen, itrile group, R
2, R
3Represent hydrogen, R
4, R
5Representative independently of one another: hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group, C
1-4Fluoro-alkyl, C
1-4Fluoroalkyl, itrile group, phenyl, amino, hexichol amido, dimethylin, diethylin, piperidines-1-base; X represents sulphur or oxygen.
4. fragrant five-membered ring substd quinolines iridium according to claim 1 (III) title complex, wherein R
1Represent hydrogen, R
2, R
3, R
4, R
5Representative independently of one another: hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group, C
1-4Fluoro-alkyl, C
1-4Fluoroalkyl, itrile group, phenyl, amino, hexichol amido, dimethylin, diethylin, piperidines-1-base; X represents sulphur or oxygen.
5. fragrant five-membered ring substd quinolines iridium according to claim 1 (III) title complex, wherein R
1Represent hydrogen, halogen, itrile group, R
3Represent hydrogen, R
2, R
4, R
5Representative independently of one another: hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group, C
1-4Fluoro-alkyl, C
1-4Fluoroalkyl, itrile group, phenyl, amino, hexichol amido, dimethylin, diethylin, piperidines-1-base; X represents sulphur or oxygen.
6. the preparation method of the described fragrant five-membered ring substd quinolines iridium of claim 1 (III) title complex, be under protection of inert gas, in the alkoxyethanol solvent system, by the fragrant five-membered ring substituted chinoline derivative part and the mol ratio of three hydration iridous chlorides according to 2-2.5:1 of general formula (II) expression, in iridium (III) the chlorine bridge dimer of 90-110 ℃ of back flow reaction acquisition respective ligand; Under protection of inert gas, in the alkoxyethanol solvent system, catalyzer anhydrous alkali metal carbonate exists down, according to the mol ratio of 1:2-2.5, obtain fragrant five-membered ring substd quinolines iridium (III) title complex in 80-110 ℃ of reaction by iridium (III) the chlorine bridge dimer of respective ligand and methyl ethyl diketone;
Wherein, R
1, R
2, R
3, R
4, R
5Representative independently of one another: hydrogen, halogen, C
1-4Alkyl, C
1-4Alkoxyl group, C
1-4Fluoro-alkyl, C
1-4Fluoroalkyl, itrile group, phenyl, amino, hexichol amido, dimethylin, diethylin, piperidines-1-base; X represents sulphur or oxygen.
7. the preparation method of fragrant five-membered ring substd quinolines iridium according to claim 6 (III) title complex, wherein the molar weight of anhydrous alkali metal carbonate be the methyl ethyl diketone molar weight 5-10 doubly, described anhydrous alkali metal carbonate is Carbon Dioxide lithium, anhydrous sodium carbonate, Anhydrous potassium carbonate, Carbon Dioxide rubidium or Carbon Dioxide caesium.
8. the preparation method of fragrant five-membered ring substd quinolines iridium according to claim 6 (III) title complex, wherein the alkoxyethanol solvent system is the mixed solvent of 2-methyl cellosolve or cellosolvo and water composition, and wherein the volume ratio of alkoxyethanol and water is 3:1.
9. claim 1,2,3,4 or 5 described fragrant five-membered ring substd quinolines iridium (III) title complexs are as the application of organic electroluminescent phosphorescence luminescent material.
10. claim 1,2,3,4 or 5 described fragrant five-membered ring substd quinolines iridium (III) title complexs are as the dopant material of organic electrophosphorescenpolymer material of main part, the application in organic electroluminescence device.
11. organic electroluminescence device, described organic luminescent device has first electrode, second electrode, and one or more layers organic function layer that between first electrode and second electrode, forms, wherein include claim 1,2,3,4 or 5 described fragrant five-membered ring substd quinolines iridium (III) title complexs in one deck organic function layer at least.
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| CN105061777A (en) * | 2015-09-17 | 2015-11-18 | 太原理工大学 | Tri-phosphor hyperbranched white light conjugated polymer and application thereof |
| CN112321444A (en) * | 2020-09-17 | 2021-02-05 | 江西邦浦医药化工有限公司 | Synthesis method of 4-bromo-3-oxo-N-phenylbutanamide |
| CN114907260A (en) * | 2022-05-27 | 2022-08-16 | 河南省科学院高新技术研究中心 | Method for preparing 4-bromomethylquinolinone by using ionic liquid |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105061777A (en) * | 2015-09-17 | 2015-11-18 | 太原理工大学 | Tri-phosphor hyperbranched white light conjugated polymer and application thereof |
| CN105061777B (en) * | 2015-09-17 | 2017-06-16 | 太原理工大学 | A kind of hyperbranched white-light conjugated polymer of three primary colours and its application |
| CN112321444A (en) * | 2020-09-17 | 2021-02-05 | 江西邦浦医药化工有限公司 | Synthesis method of 4-bromo-3-oxo-N-phenylbutanamide |
| CN114907260A (en) * | 2022-05-27 | 2022-08-16 | 河南省科学院高新技术研究中心 | Method for preparing 4-bromomethylquinolinone by using ionic liquid |
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