CN102180909A - Iridium complex phosphor material taking phthalazine derivative as ligand and preparation method thereof - Google Patents
Iridium complex phosphor material taking phthalazine derivative as ligand and preparation method thereof Download PDFInfo
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- CN102180909A CN102180909A CN201110068854XA CN201110068854A CN102180909A CN 102180909 A CN102180909 A CN 102180909A CN 201110068854X A CN201110068854X A CN 201110068854XA CN 201110068854 A CN201110068854 A CN 201110068854A CN 102180909 A CN102180909 A CN 102180909A
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Abstract
The invention discloses an iridium complex phosphor material taking a phthalazine derivative as a ligand. The structure of the material is shown as formulas (I) and (II), wherein Ar represents aryl, substituted aryl, heterocycle aryl and substituted heterocycle aryl; R can be one of a halogen atom, alkyl, substituted alkyl, alkoxyl, aryloxy, an alkylthio group, arylthio, aromatic amino, aliphatic amino or a heterocyclic substituent; L^Y can be one of N-COOH, 8-hydroxyquinoline, beta-diketone, N^NH and the like; N^N can be bipyridyl, diquinoline, 1,10-phenanthroline, a derivative of the 1,10-phenanthroline and the like; and Z can be hexafluorophosphate and perchlorate. A dicyclic or ionic iridium complex phosphorescent electroluminescent device taking the phthalazine derivative as the ligand obtained with the preparation method has high internal and external quantum yields, high luminance and high stability. A dicyclic iridium complex is shown as a formula (I), i.e., (C^N)2Ir(L^Y); and an ionic iridium complex is shown as a formula (II), i.e., (C^N)2Ir(N^N)<+>Z<->.
Description
Technical field
The present invention relates to a class luminescent material, relating to a class specifically is iridium complex phosphorescence material of part and preparation method thereof with the phthalazine derivatives
Background technology
Organic electroluminescence device has that driving voltage is low, response speed is fast, angular field of view is wide and can change luminescent properties by the chemical structure fine setting make rich color, realize easily advantages such as resolving power height, in light weight, large-area flat-plate demonstration, be described as " 21 century flat panel display ", become the focus of subjects such as material, information, physics and flat pannel display area research.Wherein, active in present organic electroluminescent research based on the electroluminescent phosphorescence luminescent material of heavy metal complex.Has d
6And d
8The heavy metal atom of electronic structure such as platinum (Pt), iridium (Ir), osmium (Os) etc., because their intensive spin orbitals coupling, make the singlet exciton and the triplet excitons of its title complex mix, triplet state has some singlet feature on the one hand, the symmetry of triplet excitons is destroyed, thereby shortening phosphorescent lifetime, make original triplet state increase the character of some singlet state, increased the intersystem crossing ability, the triplet excited state that causes prohibiting becomes the part permission to ground state transition, phosphorescence can be launched smoothly, improved luminous efficiency, internal quantum efficiency can reach 100%.
The higher phosphorescent substance of luminous efficiency is a metal iridium complex at present, and strong light emission is promptly arranged under the room temperature, illustrates that it has stronger spin orbit coupling effect.The characteristics of this class title complex are: luminous from metal to the energy of part shift (metal-to-ligand charge transfer, MLCT) or part π → π
*Transition of electron, phosphorescent lifetime is generally 1-14 μ s, being applied to device also has very high luminous efficiency.These characteristics make becomes the research focus of present electromechanical phosphorescent material to the research of complex of iridium.
When adopting phosphor material to prepare electroluminescent device as luminescence center, because it has long lifetime of excited state, when excited triplet state concentration is higher, take place easily to bury in oblivion between triplet state-triplet state and triplet state-polaron between bury in oblivion, reduce the luminous efficiency of device.For avoiding the generation of this phenomenon, can with the phosphor material object, mix in the material of main part.Usually mix less than 10% phosphorescence guest materials in the luminescent layer of phosphorescence device and occupy in 90% the host compound, the main body proportion is very large, and carrier transport is mainly born by main body.In guest materials, introduce groups such as phenyl, carbazyl, three arylamine, also can effectively improve doping content, improve carrier mobility speed, and then improve device performance.
The transition metal organic coordination compound belongs to the luminous luminescent material of part of acceptor center atom perturbation, and part plays a decisive role to its stability and photoelectric properties, therefore can obtain performance, the different phosphor material of glow color by ligand design with modification.
With the phthalazine derivatives is that ligand iridium complex is compared with the common complex of iridium that contains other C^N part, and the bond length of coordination N atom and Ir atom is shorter, and bond energy is bigger.It is easier to be synthetic and very high thermostability arranged to have the material of this structure, based on the electroluminescent device of this material is also arranged very long work-ing life.Simultaneously, the preparation cost of phthalazines luminescent material also is one of the problem that must consider of practicability.Usually when the part of synthetic complex of iridium, often need to use expensive catalysts, and severe reaction conditions, and this part preparation is simple, with low cost, it is convenient to purify, and is easy to introduce functional unit.
Summary of the invention
Technical problem: the objective of the invention is to develop and a kind ofly have advantages such as excellent photoelectric properties, stability, film-forming properties, solvability, and prepare easy, with low cost luminescent material.
Technical scheme: of the present invention is that the iridium complex phosphorescence material of part is the compound of following formula (I) or formula (II) general formula with the phthalazine derivatives:
Dicyclo complex of iridium ionic type iridium complex
(C^N)
2Ir(L^Y) (C^N)
2Ir(N^N)
+Z
-
Formula (I) formula (II)
Wherein Ar represents aryl, substituted aryl, heterocyclic aryl and substituted heterocycle aryl, and R is a kind of in halogen atom, alkyl, substituted alkyl, alkoxyl group, aryloxy, alkylthio, arylthio, fragrant amido, fat amido or the heterocyclic substituent; L^Y is wherein a kind of of N-COOH class, oxine class, beta-diketon class, N^NH; N^N is dipyridyl, diquinolyl, 1, a kind of in 10-phenanthroline and the derivative thereof; Z is hexafluoro-phosphate radical or perchlorate.
In formula (I), formula (II) general formula, aryl or substituted aryl are a kind of in benzene, biphenyl, naphthalene, acenaphthene, anthracene, phenanthrene, Bi, perylene, fluorenes, the spiral shell fluorenes; Heterocyclic aryl or substituted heterocycle aryl are a kind of in pyrroles, pyridine, furans, thiophene, carbazole, silicon fluorenes, phosphorus fluorenes, quinoline, isoquinoline 99.9, phthalazines, pyrimidine, pyridazine, pyrazine, thiodiphenylamine, acridine, dihydroketoacridine, phenanthroline, indoles, thiazole, diazole, triazole, benzodiazole, the benzothiazole; The substituting group of aryl or heterocyclic aryl is a kind of in halogen, alkyl, alkoxyl group, amino, hydroxyl, sulfydryl, ester group, boric acid ester group, acyl group, amide group, cyano group, aryloxy, aromatic base or the heterocyclic substituent, and the number of substituted aryl or substituted heterocycle aryl is single or multiple.
The preparation method comprises following synthesis step:
Formula (1) formula (2) formula (3) formula (4)
The compound of a.Ar representative is dissolved in non-polar organic solvent, in the presence of catalyzer, carries out friedel-crafts acylation reaction with Tetra hydro Phthalic anhydride under 20～80 ℃, and reaction 5h～2d obtains a class suc as formula (1) represented 2-carbonyl benzoic acid derivative;
B. 2-carbonyl benzoic acid derivative is dissolved in polar organic solvent, adds hydrazine, 20～100 ℃ are stirred 12h～5d down, obtain a class and replace phthalazines-4-ketone suc as formula (2) represented 1-;
C. 1-is replaced phthalazines-4-ketone and be dissolved in non-polar organic solvent, stir 4～48h down at 20～90 ℃, obtain a class suc as formula (3) represented 1-replacement-4-halo phthalazine compound with halide reagent;
D.1-replacement-4-halo phthalazine derivatives is dissolved in polar organic solvent, under catalyst, with the compound that contains active group by hydrocarbylation or Ullmann reaction obtain at last a class suc as formula (4) represented 1,4-two replaces phthalazine compounds;
E.IrCl
3Soluble in water, add 1,4-two replaces phthalazine compound and organic solvent, and temperature is controlled under 50～200 ℃, N
2Lucifuge stirs 8～48h in the protection, gets the dichloro endo compound of iridium;
F. the dichloro endo compound with iridium is dissolved in the organic solvent, in the effect of alkali, stirs 3～48h with assistant ligand (L^Y) down at 20～200 ℃, obtains the dicyclo metallized complex of iridium;
G. the dichloro endo compound with iridium is dissolved in the organic solvent, stirs 3～48h with corresponding assistant ligand (N^N) down at 20～200 ℃, and cooling adds salt, stirring at room, and obtaining with the phthalazine derivatives is ionic type iridium (III) title complex of part.
The reactant consumption of described step a is, by the mole umber, and 1 part of Tetra hydro Phthalic anhydride, 1～3 part of the compound of Ar representative, 10～20 parts of non-polar organic solvents, 1～5 part of catalyzer; Wherein the compound of Ar representative is aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl, and described aryl or substituted aryl are benzene, biphenyl, naphthalene, acenaphthene, anthracene, phenanthrene, Bi, perylene, fluorenes or spiral shell fluorenes; Substituted heterocycle aryl or substituted heterocycle aryl are pyrroles, pyridine, furans, thiophene, carbazole, silicon fluorenes, phosphorus fluorenes, quinoline, isoquinoline 99.9, phthalazines, pyrimidine, pyridazine, pyrazine, thiodiphenylamine, acridine, dihydroketoacridine, phenanthroline, indoles, thiazole, diazole, triazole, benzodiazole or benzothiazole; Described non-polar organic solvent is a chloroform, 1, and 2-ethylene dichloride, dithiocarbonic anhydride, tetracol phenixin, methylene dichloride, the mixture of one or more in the oil of mirbane etc.; Described catalyzer is AlCl
3, ZnCl
2, BF
3, FeCl
3Or SbF
5
The reactant consumption of described step b is, by the mole umber, and 1 part in 2-carbonyl benzoic acid derivative, 1～50 part of hydrazine, 10～80 parts of polar organic solvents, described polar organic solvent are ethanol, N, dinethylformamide, tetrahydrofuran (THF), acetone, acetonitrile or dimethyl sulfoxide (DMSO).
The reactant consumption of described step c is, by the mole umber, 1-replaces 1 part of phthalazines-4-ketone, and 1～8 part of halide reagent, 10～50 parts of non-polar organic solvents, described halide reagent are haloid acid, halogenation sulfoxide, phosphorus pentahalides, phosphorus trihalide or three oxyhalogen phosphorus; X in the formula (3) is halogen atoms such as F, Cl, Br, I; Described non-polar organic solvent is a chloroform, 1,2 ethylene dichloride, dithiocarbonic anhydride, tetracol phenixin, methylene dichloride or oil of mirbane.
The reactant consumption of described steps d is, by the mole umber, 1 part of 1-replacement-4-halogen phthalazine compound, 1～5 part of the compound that contains active group, 1～3 part of catalyzer, 5～30 parts of polar organic solvents, the described compound that contains active group is alkyl, substituted alkyl, alcohol, phenol, amine, aromatic amine or heterogeneous ring compound; Described catalyzer is mineral alkali, organic bases, salt or metal species; Described mineral alkali is salt of wormwood, saleratus, yellow soda ash or sodium bicarbonate, and described organic bases is triethylamine or pyridine, and described salt is Cu (I) salt or Cu (II) salt.
The reactant consumption of described step e is, by mole umber, IrCl
31 part, 1,4-two replaces 2～5 parts of phthalazine compounds, and 50～300 parts of organic solvents, described organic solvent are ethoxy ethanol, glycidyl ether or glycerine.
The reactant consumption of described step f is, by the mole umber, and 1 part of the dichloro endo compound of iridium, 1～5 part of assistant ligand, 1～5 part in alkali, 10～500 parts of organic solvents, described organic solvent are one or more the mixtures in methylene dichloride, ethylene glycol ethyl ether, the glycerine; Described alkali is mineral alkali or organic bases; Described mineral alkali is salt of wormwood, saleratus, yellow soda ash or sodium bicarbonate; Described organic bases is triethylamine or pyridine.
The reactant consumption of described step g is, by the mole umber, 1 part of the dichloro endo compound of iridium, 1～5 part of assistant ligand, 10～500 parts of organic solvents, 1～5 part of salt, described organic solvent are methylene dichloride, chloroform, tetracol phenixin, 1, the mixture of one or more in 2-ethylene dichloride, ethylene glycol ethyl ether, glycerine, ethanol, the methyl alcohol; Described salt is Potassium Hexafluorophosphate, ammonium hexafluorophosphate, lithium hexafluoro phosphate, sodium hexafluoro phosphate, phosphofluoric acid silver, phosphofluoric acid barium, phosphofluoric acid calcium, phosphofluoric acid magnesium, ammoniumper chlorate, potassium perchlorate, magnesium perchlorate, lithium perchlorate or sodium perchlorate.
Beneficial effect: phosphorescent iridium complex of the present invention, at first 1-is replaced phthalazines-4-ketone through halogenation treatment, improve the heterocyclic conjugated degree, and replace halogen atom with the compound that contains active group, further improve solvability, cavity transmission ability, thermostability and the film-forming properties of title complex, the introducing of these groups can produce certain steric effect in addition, thereby reduces the direct effect between the title complex luminescence center, reduce the self-quenching phenomenon of triplet exciton, improve the luminescent properties of material.The electroluminescent device that adopts this phosphorescent iridium complex to make has very high inside and outside quantum yield, luminosity and stability.
Obtained the dicyclo complex of iridium and the ionic type iridium complex of phthalazines iridium among the present invention, complex structure has been characterized by nucleus magnetic resonance, mass spectrum, infrared spectra, single crystal diffraction etc.Utilize the optical physics performance of methods such as ultraviolet, fluorescence spectrum, single photon counting method, cyclic voltammetry to them then, character such as orbital energy level are studied.The present invention has studied the luminescent properties of this micromolecular metal iridium complex and has introduced the influence of different function units to this title complex glow color and luminous efficiency.
Advantages such as complex of iridium of the present invention has good stability, solvability is good, luminous efficiency is high, synthesis technique is simple, with low cost are a kind of ruddiness phosphor materials of superior performance.
Description of drawings
Fig. 1. among the embodiment 1, ECzPQCz and (ECzPQCz)
2The uv-absorbing of Ir (Pic) in methylene dichloride and (ECzPQCz)
2The fluorescence emission spectrum of Ir (Pic).
Fig. 2. among the embodiment 3, TPAPQCz and (TPAPQCz)
2The uv-absorbing of Ir (Pic) in methylene dichloride and (TPAPQCz)
2The fluorescence emission spectrum of Ir (Pic).
Fig. 3. among the embodiment 4, TPAPQPz and (TPAPQPz)
2The uv-absorbing of Ir (Pic) in methylene dichloride and (TPAPQPz)
2The fluorescence emission spectrum of Ir (Pic).
Embodiment
Phosphorescent iridium complex of the present invention is to form dicyclo metal iridium complex (C^N) with phthalazine derivatives and metal iridium (III) coordination
2Ir (L^Y) or ionic title complex (C^N)
2Ir (N^N)
+Z
-, its structure can be represented by formula (I) or formula (II):
Dicyclo complex of iridium ionic type iridium complex
(C^N)
2Ir(L^Y) (C^N)
2Ir(N^N)
+Z
-
Formula (I) formula (II)
Wherein R can be a kind of in halogen atom, alkyl, substituted alkyl, alkoxyl group, aryloxy, alkylthio, arylthio, fragrant amido, fat amido or the heterocyclic substituent; Ar represents aryl, substituted aryl, heterocyclic aryl and substituted heterocycle aryl.Aryl or substituted aryl can be aromatic compounds such as benzene, biphenyl, naphthalene, acenaphthene, anthracene, phenanthrene, Bi, perylene, fluorenes, spiral shell fluorenes and contain its substituent derivative.Heterocyclic aryl or substituted heterocycle aryl can be heterocyclic aromatic compounds such as pyrroles, pyridine, furans, thiophene, carbazole, silicon fluorenes, phosphorus fluorenes, quinoline, isoquinoline 99.9, phthalazines, pyrimidine, pyridazine, pyrazine, thiodiphenylamine, acridine, dihydroketoacridine, phenanthroline, indoles, thiazole, diazole, triazole, benzodiazole, benzothiazole and contain substituent derivative.The substituting group of aryl or heterocyclic aryl can be halogen, alkyl, alkoxyl group, amino, hydroxyl, sulfydryl, ester group, boric acid ester group, acyl group, amide group, cyano group, aryloxy, aromatic base or heterocyclic substituent etc.The substituent number of aryl or heterocyclic aryl can be for single or multiple.L^Y can be wherein a kind of such as N-COOH class, oxine class, beta-diketon class, N^NH; N^N can be dipyridyl, diquinolyl, 1,10-phenanthroline and derivative thereof etc.; Z can be hexafluoro-phosphate radical, perchlorate etc.
The preparation method of phosphorescent iridium complex of the present invention is characterized in that comprising the steps:
Formula (1) formula (2) formula (3) formula (4)
(1) compound of Ar representative is dissolved in non-polar organic solvent, in the presence of catalyzer, carries out friedel-crafts acylation reaction with Tetra hydro Phthalic anhydride under 20～80 ℃, and reaction 5h～2d obtains a class suc as formula (1) represented 2-carbonyl benzoic acid derivative;
(2) 2-carbonyl benzoic acid derivative is dissolved in polar organic solvent, adds hydrazine, 20～100 ℃ are stirred 12h～5d down, obtain a class and replace phthalazines-4-ketone suc as formula (2) represented 1-;
(3) 1-is replaced phthalazines-4-ketone and be dissolved in non-polar organic solvent, stir 4～48h down at 20～90 ℃, obtain a class suc as formula (3) represented 1-replacement-4-halo phthalazine compound with halide reagent;
(4) 1-replacement-4-halo phthalazine derivatives is dissolved in polar organic solvent, under catalyst, with the compound that contains active group by hydrocarbylation or Ullmann reaction obtain at last a class suc as formula (4) represented 1,4-two replaces phthalazine compounds;
(5) IrCl
3Soluble in water, add 1,4-two replaces phthalazine compound and organic solvent, and temperature is controlled under 50～200 ℃, N
2Lucifuge stirs 8～48h in the protection, gets the dichloro endo compound of iridium;
(6) preparation of dicyclo metallized complex of iridium: the dichloro endo compound of iridium is dissolved in the organic solvent,, stirs 3～48h down at 20～200 ℃, obtain the dicyclo metal iridium complex with assistant ligand (L^Y) in the effect of alkali;
(7) preparation of ionic type iridium complex: the dichloro endo compound of iridium is dissolved in the organic solvent, stirs 3～48h with corresponding assistant ligand (N^N) down at 20～200 ℃, cooling adds salt, and stirring at room obtains ionic type iridium (III) title complex.
The preparation method's of phthalazines complex of iridium optimum condition is:
The reactant consumption of step (1) is, by the mole umber, 1 part of Tetra hydro Phthalic anhydride, 1～3 part of aryl or heterocyclic aryl, 10～20 parts of non-polar organic solvents, 1～5 part of Lewis acid, wherein the compound of Ar representative can be an aryl, replace aryl, heterocyclic aryl and substituted heterocycle aryl, described aryl or substituted aryl can be benzene, biphenyl, naphthalene, acenaphthene, anthracene, luxuriant and rich with fragrance, pyrene perylene, fluorenes, aromatic compounds such as spiral shell fluorenes and contain its substituent derivative, heterocyclic aryl or substituted heterocycle aryl can be the pyrroles, pyridine, furans, thiophene, carbazole, the silicon fluorenes, the phosphorus fluorenes, quinoline, isoquinoline 99.9, phthalazines, pyrimidine, pyridazine, pyrazine, thiodiphenylamine, acridine, dihydroketoacridine, phenanthroline, indoles, thiazole, diazole, triazole, benzodiazole, heteroaromaticizations such as benzothiazole; Described non-polar organic solvent can be a chloroform, 1, and 2-ethylene dichloride, dithiocarbonic anhydride, tetracol phenixin, methylene dichloride, the mixture of one or more in the oil of mirbane etc.; Described Lewis acid can be AlCl
3, ZnCl
2, BF
3, FeCl
3, SbF
5Deng.
The reactant consumption of step (2) is, by the mole umber, and 1 part in 2-carbonyl benzoic acid derivative, 1～50 part of hydrazine, 10～80 parts of polar organic solvents, described polar organic solvent can be ethanol, N, dinethylformamide, tetrahydrofuran (THF), acetone, acetonitrile or dimethyl sulfoxide (DMSO) etc.
The reactant consumption of step (3) is, by the mole umber, 1-replaces 1 part of phthalazines-4-ketone, 1～8 part of halide reagent, 10～50 parts of non-polar organic solvents, described halide reagent can be haloid acid, halogenation sulfoxide, phosphorus pentahalides, phosphorus trihalide, three oxyhalogen phosphorus etc.; X in the formula (3) is halogen atoms such as F, Cl, Br, I; Described non-polar organic solvent can be a chloroform, 1,2 ethylene dichloride, dithiocarbonic anhydride, tetracol phenixin, methylene dichloride, oil of mirbane etc.
The reactant consumption of step (4) is, by the mole umber, 1 part of 1-replacement-4-halogen phthalazine compound, 1～5 part of the compound that contains active group, 1～3 part of catalyzer, 5～30 parts of polar organic solvents, the described compound that contains active group can be alkyl, substituted alkyl, alcohol, phenol, amine, aromatic amine, heterogeneous ring compound etc.; Described catalyzer is mineral alkali, organic bases, salt or metal species etc., described mineral alkali can be salt of wormwood, saleratus, yellow soda ash, sodium bicarbonate etc., described organic bases can be triethylamine, pyridine etc., and described salt can be Cu (I) salt, Cu (II) salt etc.
The reactant consumption of step (5) is, by mole umber, IrCl
31 part, 1,4-two replaces 2～5 parts of phthalazine compounds, and 50～300 parts of organic solvents, described organic solvent are ethoxy ethanol, glycidyl ether, glycerine etc.
The reactant consumption of step (6) is, by the mole umber, and 1 part of the dichloro endo compound of iridium, 1～5 part of assistant ligand, 1～5 part in alkali, 10～500 parts of organic solvents, described organic solvent can be one or more mixtures wherein such as methylene dichloride, ethylene glycol ethyl ether, glycerine; Described alkali can be mineral alkali and organic bases; Described mineral alkali can be salt of wormwood, saleratus, yellow soda ash, sodium bicarbonate etc.; Described organic bases can be triethylamine, pyridine etc.
The reactant consumption of step (7) is, by the mole umber, 1 part of the dichloro endo compound of iridium, 1～5 part of assistant ligand, 10～500 parts of organic solvents, 1～5 part of salt, described organic solvent can be methylene dichloride, chloroform, tetracol phenixin, 1, one or more mixture wherein such as 2-ethylene dichloride, ethylene glycol ethyl ether, glycerine, ethanol, methyl alcohol; Described salt can be Potassium Hexafluorophosphate, ammonium hexafluorophosphate, lithium hexafluoro phosphate, sodium hexafluoro phosphate, phosphofluoric acid silver, phosphofluoric acid barium, phosphofluoric acid calcium, phosphofluoric acid magnesium etc., ammoniumper chlorate, potassium perchlorate, magnesium perchlorate, lithium perchlorate, sodium perchlorate etc.
Following examples are to further specify of the present invention, are not limitations of the present invention.
Embodiment 1:
Take by weighing 2.78g (21mmol) AlCl
3, 2.31g (15.6mmol) Tetra hydro Phthalic anhydride adds the stirring of 10ml (156mmol) methylene dichloride ice bath and makes its dissolving in two-mouth bottle.Take by weighing 3.56g (18mmol) N-ethyl-9H-carbazole in the single port bottle, add 10ml (156mmol) methylene dichloride stirring at room, slowly drip above-mentioned mixed solution, continue stirred overnight at room temperature with separating funnel.Reaction finishes, and adds rare HCl and transfer to slightly acidic in reaction solution, adds suitable quantity of water, chloroform extraction, and the organic phase washing merges organic phase, anhydrous MgSO
4Drying is crossed column purification and is got 2-(9-ethyl-9H-carbazole-3-carbonyl) phenylformic acid.
Add 1.01g (2.9mmol) 2-(ethyl carbazole formyl)-phenylformic acid in the two-mouth bottle, N
2Hydrazine hydrate and 10ml (171mmol) ethanol of 5ml (129mmol) 80%, reflux 12h are injected in protection down.Reaction finishes, and is cooled to room temperature, and the adularescent precipitation is separated out, and filters washing with alcohol, dry 4-(9-ethyl-9H-carbazole-3-yl) phthalazines-1 (2H)-ketone that gets.
Add 2.0g (5.9mmol) 4-(N-ethyl) carbazole-1-phthalazone in the two-mouth bottle, N
2Protection adds 20ml (250mmo) CHCl down
3And 3ml (32.7mmol) POCl
3Be warming up to 60 ℃ of reaction 12h.Reaction finishes, and reaction solution is poured in the 400g water, and weak ammonia transfers PH to weakly alkaline, has solid to separate out, and filters, and the acetic acid ethyl dissolution solid is crossed column purification and got 3-(4-chlorine phthalazines-1-yl)-9-ethyl-9H-carbazole.
Take by weighing NaH and the two-mouth bottle of 1.00g (6mmol) carbazole and 0.31g (7mmol) 65%, N
2The anhydrous N of 5ml (65mmol), dinethylformamide, stirring at room 1h are injected in protection down; 1.79g (5mmol) 3-(4-chlorine phthalazines-1-yl)-9-ethyl-9H-carbazole is dissolved in 5ml (65mmol) N; in the dinethylformamide, slowly splash into reaction flask, continue stirred overnight at room temperature.Reaction solution is poured in the big water gaging, and ethyl acetate extraction is crossed column purification and is got 3-(4-(9H-carbazole-9-yl) phthalazines-1-yl)-9-ethyl-9H-carbazole.
Take by weighing 0.146g (0.3mmol) 3-(4-(9H-carbazole-9-yl) phthalazines-1-yl)-9-ethyl-9H-carbazole and 0.035g (0.1mmol) IrCl
3H
2O injects 1ml (55mmol) water and 3ml (31mmol) ethylene glycol ethyl ether, N in two-mouth bottle
2Be warming up to 80 ℃ of reaction 24h under the protection, be cooled to room temperature, filter, difference water, washing with alcohol solid, the dry dichloro endo compound that gets iridium.
The dichloro endo compound that takes by weighing 0.1g (0.042mmol) iridium is dissolved in 5ml (78mmol) methylene dichloride, add 0.015g (0.126mmol) pyridine carboxylic acid and 0.017g (0.126mmol) salt of wormwood, be warming up to 60 ℃ and stir 12h, cooling is crossed column purification and is got complex of iridium (ECzPQCz)
2Ir (Pic).
Embodiment 2:
Take by weighing NaH and the two-mouth bottle of 1.01g (6mmol) pentanoic and 0.31g (7mmol) 65%, N
2The anhydrous N of 5ml (65mmol), dinethylformamide, stirring at room 1h are injected in protection down; 1.79g (5mmol) 3-(4-chlorine phthalazines-1-yl)-9-ethyl-9H-carbazole is dissolved in 5ml (65mmol) N; in the dinethylformamide, slowly splash into reaction flask, continue stirred overnight at room temperature.Reaction solution is poured in the big water gaging, ethyl acetate extraction, dry organic phase concentrates, and crosses column purification and gets 4-(9-ethyl-9H-carbazole-3-yl)-N, N-phenylbenzene phthalazines-1-amine.
Take by weighing 0.147g (0.3mmol) 4-(9-ethyl-9H-carbazole-3-yl)-N, N-phenylbenzene phthalazines-1-amine and 0.035g (0.1mmol) IrCl
3H
2O injects 1ml (55mmol) water and 3ml (31mmol) ethylene glycol ethyl ether, N in two-mouth bottle
2Be warming up to 80 ℃ of reaction 24h under the protection, be cooled to room temperature, filter, difference water, washing with alcohol solid, the dry dichloro endo compound that gets iridium.
The dichloro endo compound that takes by weighing 0.101g (0.042mmol) iridium is dissolved in 5ml (78mmol) methylene dichloride, add 0.015g (0.126mmol) methyl ethyl diketone sodium salt and 0.017g (0.126mmol) salt of wormwood, be warming up to 60 ℃ and stir 12h, cooling is crossed column purification and is got complex of iridium (ECzPQDPA)
2Ir (acac).
Embodiment 3:
Take by weighing 1.94g (14.5mmol) AlCl
3, 0.61g (4.12mmol) Tetra hydro Phthalic anhydride adds 15ml (234mmol) CH in two-mouth bottle
2Cl
2Ice bath stirs and makes its dissolving, stirs down to add 1.23g (5mmol) triphenylamine, continues stirred overnight at room temperature.Reaction finishes, and adds rare HCl and transfer to slightly acidic in reaction solution, and chloroform extraction merges organic phase, anhydrous MgSO
4Drying is crossed column purification and is got 2-(4-(diphenyl amino) benzoyl) phenylformic acid.
Add 1.14g (2.9mmol) 2-(4-(diphenyl amino) benzoyl) phenylformic acid in the two-mouth bottle, N
2Hydrazine hydrate and 10ml (171mmol) ethanol of an amount of 5ml (129mmol) 80%, reflux 12h are injected in protection down.Reaction finishes, and is cooled to room temperature, has yellow mercury oxide to separate out, and filters washing with alcohol, dry 4-(4-(diphenyl amino) phenyl) phthalazines-1 (2H)-ketone that gets.
Take by weighing 5.13g (13mmol) 4-(4-(diphenyl amino) phenyl) phthalazines-1 (2H)-ketone in two-mouth bottle, N
215ml (187mmol) CHCl is injected in protection down
3And 3ml (33mmol) POCl
3, be warming up to 60 ℃ and stir 8h, be cooled to room temperature, decompression steams CHCl
3, residuum to be poured in the water, weak ammonia is adjusted to weakly alkaline, has solid to produce, and crosses column purification and gets 4-(4-chlorine phthalazines-1-yl)-N, N-phenylbenzene aniline.
Take by weighing NaH and the two-mouth bottle of 1.17g (7mmol) carbazole and 0.32g (8mmol) 65%, N
2The anhydrous N of 5ml (65mmol), dinethylformamide, stirring at room 1h are injected in protection down; with 2.04g (5mmol) 4-(4-chlorine phthalazines-1-yl)-N, N-phenylbenzene aniline is dissolved in the anhydrous N of 5ml (65mmol), in the dinethylformamide; slowly splash into reaction flask, dropwise, stirred overnight at room temperature.Reaction solution is poured in the big water gaging, ethyl acetate extraction, dry organic phase is crossed column purification and is got 4-(4-(9H-carbazole-9-yl) phthalazines-1-yl)-N, N-phenylbenzene aniline.
Take by weighing 0.164g (0.3mmol) 4-(4-(9H-carbazole-9-yl) phthalazines-1-yl)-N, N-phenylbenzene aniline and 0.035g (0.1mmol) IrCl
3H
2O injects 1ml (55mmol) water and 3ml (31mmol) 7 glycol ethers, N in two-mouth bottle
2Be warming up to 80 ℃ of reaction 24h under the protection, be cooled to room temperature, filter, difference water, washing with alcohol solid, the dry dichloro endo compound that gets iridium.
The dichloro endo compound 0.109g (0.042mmol) of the above-mentioned iridium of exsiccant is dissolved in 5ml (78mmol) methylene dichloride, add 0.015g (0.126mmol) pyridine carboxylic acid and 0.017g (0.126mmol) salt of wormwood, be warming up to 50 ℃ and stir 12h, cooling, concentrate, cross column purification and get (TPAPQCz)
2Ir (Pic).
Embodiment 4:
Take by weighing NaH and the two-mouth bottle of 1.39g (7mmol) thiodiphenylamine and 0.32g (8mmol) 65%, N
2The anhydrous N of 5ml (65mmol), dinethylformamide, stirring at room 1h are injected in protection down; with 2.04g (5mmol) 4-(4-chlorine phthalazines-1-yl)-N, N-phenylbenzene aniline is dissolved in the anhydrous N of 5ml (65mmol), in the dinethylformamide; slowly splash into reaction flask, dropwise, stirred overnight at room temperature.Reaction solution is poured in the big water gaging, ethyl acetate extraction, dry organic phase is crossed column purification and is got 4-(4-(10H-benzothiazine-10-yl) phthalazines-1-yl)-N, N-phenylbenzene aniline.
Take by weighing 0.171g (0.3mmol) 4-(4-(10H-benzothiazine-10-yl) phthalazines-1-yl)-N, N-phenylbenzene aniline and 0.035g (0.1mmol) IrCl
3H
2O injects 1ml (55mmol) water and 3ml (31mmol) ethylene glycol ethyl ether, N in two-mouth bottle
2Be warming up to 80 ℃ of reaction 24h under the protection, be cooled to room temperature, filter, difference water, washing with alcohol solid, the dry dichloro endo compound that gets iridium.
The dichloro endo compound 0.114g (0.042mmol) of the above-mentioned iridium of exsiccant is dissolved in 5ml (78mmol) methylene dichloride, add 0.015g (0.126mmol) pyridine carboxylic acid and 0.017g (0.126mmol) salt of wormwood, be warming up to 50 ℃ and stir 12h, cooling, concentrate, cross column purification and get (TPAPQPz)
2Ir (Pic).
Embodiment 5:
0.114g (0.042mmol) dichloro endo compound is dissolved in 5ml (63mmol) 1, in 2-ethylene dichloride and 3ml (51mmol) ethanol mixed solvent, add 0.08g (0.28mmol) 1, the 10-phenanthroline, being warming up to refluxes stirs 8h, reaction is cooled to room temperature after finishing, and adds 0046g (0.28mmol) ammonium hexafluorophosphate, stirring at room 2h, steam solvent, solid is dissolved in methylene dichloride, and the mistake column purification obtains the iridium that negatively charged ion is a hexafluoro-phosphate radical (III), and title complex [(TPAPQPz)
2Ir (N^N)]
+(PF
6)
-
Claims (10)
1. one kind is the iridium complex phosphorescence material of part with the phthalazine derivatives, it is characterized in that this material is the compound of following formula (I) or formula (II) general formula:
Dicyclo complex of iridium ionic type iridium complex
(C^N)
2Ir(L^Y) (C^N)
2Ir(N^N)
+Z
-
Formula (I) formula (II)
Wherein Ar represents aryl, substituted aryl, heterocyclic aryl and substituted heterocycle aryl, and R is a kind of in halogen atom, alkyl, substituted alkyl, alkoxyl group, aryloxy, alkylthio, arylthio, fragrant amido, fat amido or the heterocyclic substituent; L^Y is wherein a kind of of N-COOH class, oxine class, beta-diketon class, N^NH; N^N is dipyridyl, diquinolyl, 1, a kind of in 10-phenanthroline and the derivative thereof; Z is hexafluoro-phosphate radical or perchlorate.
2. according to claim 1 is the iridium complex phosphorescence material of part with the phthalazine derivatives, it is characterized in that in formula (I), formula (II) general formula aryl or substituted aryl are a kind of in benzene, biphenyl, naphthalene, acenaphthene, anthracene, phenanthrene, Bi, perylene, fluorenes, the spiral shell fluorenes; Heterocyclic aryl or substituted heterocycle aryl are a kind of in pyrroles, pyridine, furans, thiophene, carbazole, silicon fluorenes, phosphorus fluorenes, quinoline, isoquinoline 99.9, phthalazines, pyrimidine, pyridazine, pyrazine, thiodiphenylamine, acridine, dihydroketoacridine, phenanthroline, indoles, thiazole, diazole, triazole, benzodiazole, the benzothiazole; The substituting group of aryl or heterocyclic aryl is a kind of in halogen, alkyl, alkoxyl group, amino, hydroxyl, sulfydryl, ester group, boric acid ester group, acyl group, amide group, cyano group, aryloxy, aromatic base or the heterocyclic substituent, and the number of substituted aryl or substituted heterocycle aryl is single or multiple.
One kind as claimed in claim 1 be the iridium complex phosphorescence preparation methods of part with the phthalazine derivatives, it is characterized in that the preparation method comprises following synthesis step:
Formula (1) formula (2) formula (3) formula (4)
The compound of a.Ar representative is dissolved in non-polar organic solvent, in the presence of catalyzer, carries out friedel-crafts acylation reaction with Tetra hydro Phthalic anhydride under 20～80 ℃, and reaction 5h～2d obtains a class suc as formula (1) represented 2-carbonyl benzoic acid derivative;
B. 2-carbonyl benzoic acid derivative is dissolved in polar organic solvent, adds hydrazine, 20～100 ℃ are stirred 12h～5d down, obtain a class and replace phthalazines-4-ketone suc as formula (2) represented 1-;
C. 1-is replaced phthalazines-4-ketone and be dissolved in non-polar organic solvent, stir 4～48h down at 20～90 ℃, obtain a class suc as formula (3) represented 1-replacement-4-halo phthalazine compound with halide reagent;
D.1-replacement-4-halo phthalazine derivatives is dissolved in polar organic solvent, under catalyst, with the compound that contains active group by hydrocarbylation or Ullmann reaction obtain at last a class suc as formula (4) represented 1,4-two replaces phthalazine compounds;
E.IrCl
3Soluble in water, add 1,4-two replaces phthalazine compound and organic solvent, and temperature is controlled under 50～200 ℃, N
2Lucifuge stirs 8～48h in the protection, gets the dichloro endo compound of iridium;
F. the dichloro endo compound with iridium is dissolved in the organic solvent, in the effect of alkali, stirs 3～48h with assistant ligand (L^Y) down at 20～200 ℃, obtains the dicyclo metallized complex of iridium;
G. the dichloro endo compound with iridium is dissolved in the organic solvent, stirs 3～48h with corresponding assistant ligand (N^N) down at 20～200 ℃, and cooling adds salt, stirring at room, and obtaining with the phthalazine derivatives is ionic type iridium (III) title complex of part.
4. according to claim 3 is the iridium complex phosphorescence preparation methods of part with the phthalazine derivatives, the reactant consumption that it is characterized in that described step a is, by the mole umber, 1 part of Tetra hydro Phthalic anhydride, 1～3 part of the compound of Ar representative, 10～20 parts of non-polar organic solvents, 1～5 part of catalyzer; Wherein the compound of Ar representative is aryl, substituted aryl, heterocyclic aryl or substituted heterocycle aryl, and described aryl or substituted aryl are benzene, biphenyl, naphthalene, acenaphthene, anthracene, phenanthrene, Bi, perylene, fluorenes or spiral shell fluorenes; Substituted heterocycle aryl or substituted heterocycle aryl are pyrroles, pyridine, furans, thiophene, carbazole, silicon fluorenes, phosphorus fluorenes, quinoline, isoquinoline 99.9, phthalazines, pyrimidine, pyridazine, pyrazine, thiodiphenylamine, acridine, dihydroketoacridine, phenanthroline, indoles, thiazole, diazole, triazole, benzodiazole or benzothiazole; Described non-polar organic solvent is a chloroform, 1, and 2-ethylene dichloride, dithiocarbonic anhydride, tetracol phenixin, methylene dichloride, the mixture of one or more in the oil of mirbane etc.; Described catalyzer is AlCl
3, ZnCl
2, BF
3, FeCl
3Or SbF
5
5. according to claim 3 is the iridium complex phosphorescence preparation methods of part with the phthalazine derivatives, the reactant consumption that it is characterized in that described step b is, by the mole umber, 1 part in 2-carbonyl benzoic acid derivative, 1～50 part of hydrazine, 10～80 parts of polar organic solvents, described polar organic solvent are ethanol, N, dinethylformamide, tetrahydrofuran (THF), acetone, acetonitrile or dimethyl sulfoxide (DMSO).
6. according to claim 3 is the iridium complex phosphorescence preparation methods of part with the phthalazine derivatives, the reactant consumption that it is characterized in that described step c is, by the mole umber, 1-replaces 1 part of phthalazines-4-ketone, 1～8 part of halide reagent, 10～50 parts of non-polar organic solvents, described halide reagent are haloid acid, halogenation sulfoxide, phosphorus pentahalides, phosphorus trihalide or three oxyhalogen phosphorus; X in the formula (3) is halogen atoms such as F, Cl, Br, I; Described non-polar organic solvent is a chloroform, 1,2 ethylene dichloride, dithiocarbonic anhydride, tetracol phenixin, methylene dichloride or oil of mirbane.
7. according to claim 3 is the iridium complex phosphorescence preparation methods of part with the phthalazine derivatives, the reactant consumption that it is characterized in that described steps d is, by the mole umber, 1 part of 1-replacement-4-halogen phthalazine compound, 1～5 part of the compound that contains active group, 1～3 part of catalyzer, 5～30 parts of polar organic solvents, the described compound that contains active group is alkyl, substituted alkyl, alcohol, phenol, amine, aromatic amine or heterogeneous ring compound; Described catalyzer is mineral alkali, organic bases, salt or metal species; Described mineral alkali is salt of wormwood, saleratus, yellow soda ash or sodium bicarbonate, and described organic bases is triethylamine or pyridine, and described salt is Cu (I) salt or Cu (II) salt.
8. according to claim 3 is the iridium complex phosphorescence preparation methods of part with the phthalazine derivatives, it is characterized in that the reactant consumption of described step e is, by mole umber, IrCl
31 part, 1,4-two replaces 2～5 parts of phthalazine compounds, and 50～300 parts of organic solvents, described organic solvent are ethoxy ethanol, glycidyl ether or glycerine.
9. according to claim 3 is the iridium complex phosphorescence preparation methods of part with the phthalazine derivatives, the reactant consumption that it is characterized in that described step f is, by the mole umber, 1 part of the dichloro endo compound of iridium, 1～5 part of assistant ligand, 1～5 part in alkali, 10～500 parts of organic solvents, described organic solvent are one or more the mixtures in methylene dichloride, ethylene glycol ethyl ether, the glycerine; Described alkali is mineral alkali or organic bases; Described mineral alkali is carbonic acid clock, saleratus, yellow soda ash or sodium bicarbonate; Described organic bases is triethylamine or pyridine.
10. according to claim 3 is the iridium complex phosphorescence preparation methods of part with the phthalazine derivatives, the reactant consumption that it is characterized in that described step g is, by the mole umber, 1 part of the dichloro endo compound of iridium, 1～5 part of assistant ligand, 10～500 parts of organic solvents, 1～5 part of salt, described organic solvent is methylene dichloride, chloroform, tetracol phenixin, 1, the mixture of one or more in 2-ethylene dichloride, ethylene glycol ethyl ether, glycerine, ethanol, the methyl alcohol; Described salt is Potassium Hexafluorophosphate, ammonium hexafluorophosphate, lithium hexafluoro phosphate, sodium hexafluoro phosphate, phosphofluoric acid silver, phosphofluoric acid barium, phosphofluoric acid calcium, phosphofluoric acid magnesium, ammoniumper chlorate, potassium perchlorate, magnesium perchlorate, lithium perchlorate or sodium perchlorate.
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