CN104418899A - Organic iridium metal complex and preparation method and application thereof - Google Patents

Organic iridium metal complex and preparation method and application thereof Download PDF

Info

Publication number
CN104418899A
CN104418899A CN201310367782.8A CN201310367782A CN104418899A CN 104418899 A CN104418899 A CN 104418899A CN 201310367782 A CN201310367782 A CN 201310367782A CN 104418899 A CN104418899 A CN 104418899A
Authority
CN
China
Prior art keywords
metal complex
iridium metal
organic
reaction
organic iridium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201310367782.8A
Other languages
Chinese (zh)
Inventor
周明杰
王平
张娟娟
黄辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Original Assignee
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oceans King Lighting Science and Technology Co Ltd, Shenzhen Oceans King Lighting Engineering Co Ltd filed Critical Oceans King Lighting Science and Technology Co Ltd
Priority to CN201310367782.8A priority Critical patent/CN104418899A/en
Publication of CN104418899A publication Critical patent/CN104418899A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0033—Iridium compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd

Abstract

The invention discloses an organic iridium metal complex and a preparation method and an application thereof. A molecular structure general formula of the organic iridium metal complex is shown in (I), wherein, at least one group of R1, R2, R3 in (I) is alkoxy or/and aromatic group. The preparation method comprises the steps of preparing a chlorine bridge biopolymer and using the chlorine bridge biopolymer to prepare the organic iridium metal complex with the structure general formula (I). The above organic iridium metal complex takes 2-(3'-cyan-4'-fluorophenyl)pyrimidine as a main structure of an iridium metal ligand, and the organic iridium metal complex has high blue light purity and luminescence efficiency, and the organic iridium metal complex has high blue light purity and luminescence efficiency.

Description

Organic iridium metal complex and its preparation method and application
Technical field
The invention belongs to organic electromechanical phosphorescent material technical field, relate to a kind of organic iridium metal complex and its preparation method and application specifically.
Background technology
Organic electroluminescent refers to that organic materials is under electric field action, electric energy is converted into a kind of luminescence phenomenon of luminous energy.Make to stay cool to the research of organic electroluminescent due to reasons such as the driving voltage of organic electroluminescence device are too high, luminous efficiency is very low in early days.Until 1987, the human hairs such as the Tang of Kodak understand with oxine aluminium (Alq3) for luminescent material, the high-quality thin film of even compact is made with aromatic diamine, obtain low-work voltage, high brightness, high efficiency organic electroluminescence device, open the new prelude to electroluminescent organic material research.But owing to being subject to the restriction of spin statistics theory, the theoretical internal quantum efficiency limit of fluorescent material is only 25%, how makes full use of all the other phosphorescence of 75% and realize higher luminous efficiency and become hot research direction in after this this field.1997, Forrest etc. found electrophosphorescence phenomenon, and the internal quantum efficiency of electroluminescent organic material breaches the restriction of 25%, makes the research of electroluminescent organic material enter another new period.
In research subsequently, the title complex of small molecules doping type transition metal has become the research emphasis of people, as the title complex of iridium, ruthenium, platinum etc.The advantage of this kind of title complex is that they can obtain very high emitted energy from the triplet state of self, and wherein metal iridium (III) compound, due to good stability, in building-up process, reaction conditions is gentle, and there is very high electroluminescent properties, in research process subsequently, account for dominant position always.And in order to make device obtain full-color display, generally must obtain the ruddiness of excellent performance, green glow and blue light material simultaneously.Compare with green light material with ruddiness, the development of blue light material is more delayed comparatively speaking, the breakthrough point that the efficiency improving blue light material has just become people to study with purity of color.
So far, constantly deeply, but there is bottleneck problem to the research of organic electromechanical phosphorescent material iridium metal complex in people in the efficiency decay etc. of the illuminant colour purity of blue emitting phosphor material, luminous efficiency and device.Its major cause be the title complex of existing iridium metals ion on the one hand due to cyclic metal complexes agent structure itself, have impact on the luminescence of phosphor material; On the other hand, easily there is direct effect between the atoms metal in the title complex of metal ion and cause the generation of the self-quenching phenomenon of triplet exciton, thus having had a strong impact on the electroluminescent properties of phosphorescent light-emitting materials.Therefore, the blue phosphorescent organic electroluminescent material how developing high color purity and luminous efficiency becomes the technical barrier expanded blue light material and apply in electroluminescent device.
Summary of the invention
The object of the invention is to the above-mentioned deficiency overcoming prior art, a kind of organic iridium metal complex is provided, to solve existing organic iridium metal complex blue light color purity and the not high technical problem of luminous efficiency.
Another object of the present invention is to provide a kind of productive rate high, the organic iridium metal complex preparation method be easy to operate and control.
Another object of the present invention is the application providing above-mentioned organic iridium metal complex.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of organic iridium metal complex, its general formula of molecular structure is following (I):
In formula, R 1, R 2, R 3in at least one group be that alkoxyl group is or/and aromatic group.
And a kind of preparation method of organic iridium metal complex, comprises the steps:
The compd A of following structural formula general formula is provided:
In the environment of anaerobic, described compd A and hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium are carried out thermal backflow reaction in reaction solvent, generate the chlorine bridge dipolymer B of following structural formula general formula:
In the environment of anaerobic, by described chlorine bridge dipolymer B and 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole is under sodium methylate and/or sodium ethylate catalyst action and carry out thermal backflow reaction in reaction solvent, purifying, obtains organic iridium metal complex of following general formula of molecular structure (I):
Wherein, the R in compd A, B and general structure (I) 1, R 2, R 3in at least one group be that alkoxyl group is or/and aromatic group.
And above-mentioned organic iridium metal complex is as the application of blue electrophosphorescence material in organic electroluminescence device, EL cold light film or electrochemical cell luminescent device.
Above-mentioned organic iridium metal complex is cyclic metal complexes agent structure with 2-(3'-cyano group-4'-fluorophenyl) pyrimidine, and with 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole is assistant ligand, gives the high blue light color purity of this organic iridium metal complex and luminous efficiency.Wherein, pyrimidine group on 2-(3'-cyano group-4'-fluorophenyl) the main part of pyrimidine is conducive to the lumo energy improving this organic iridium metal complex, on phenyl ring, two strong electron-withdrawing group F bases and cyano group are conducive to the HOMO energy level reducing this organic iridium metal complex, make the effective blue shift of material emission wavelength; Alkoxyl group or and aromatic group be electron-donating group, pyrimidine ring introduce alkoxyl group or and aromatic group, this organic iridium metal complex can launch blue light, the long aliphatic chain of alkoxyl group and the aromatic group of large volume can produce larger space steric effect on the one hand in addition, the direct effect between atoms metal can be stoped, the self-quenching phenomenon of remarkable reduction triplet exciton, thus the luminous efficiency improving material; On phenyl ring, the introducing of strong electron-withdrawing group fluorine-based, the cyano group of group and high field intensity assistant ligand 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles can also improve luminescent properties, is beneficial to evaporation, increases film-forming properties and improves the stability of device.
Above-mentioned organic iridium metal complex preparation method only needs 2-3 to walk the reaction of ripe type, and target product is easily deducted a percentage, and productive rate is high, and its reaction is easy to operate and control, and is suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the schema of the organic iridium metal complex preparation method of the embodiment of the present invention;
Fig. 2 be embodiment 1 prepare two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-phenyl pyrimidine-N, C 2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close the spectroscopic analysis figure of iridium metal complex;
Fig. 3 is two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-phenyl pyrimidine-N, the C that prepare with embodiment 1 2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close the OLED structure schematic diagram that iridium metal complex is electroluminescent organic material.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides and a kind ofly have blue light color purity and the high organic iridium metal complex of luminous efficiency, its general formula of molecular structure is following (I):
Particularly, the R in (I) formula 1, R 2, R 3in at least one group be that alkoxyl group is or/and aromatic group.Therefore, this general formula of molecular structure (I) organic iridium metal complex at least has following several molecular structural formula:
Ra, Rb, Rc in above-mentioned I 1 to I 7 molecular structural formula are that identical or not identical alkoxyl group is or/and aromatic group.
Lead in organic iridium metal complex of formula I at said structure, on pyrimidine ring, the introducing of at least one alkoxyl group or aromatic group mainly has the effect of following aspect:
1. alkoxyl group or and aromatic group be electron-donating group, pyrimidine ring introduce alkoxyl group or and aromatic group, this organic iridium metal complex can launch blue light;
2. increase the branch arm of this organic iridium metal complex, thus increase the three-dimensional space steric effect of this organic iridium metal complex, stop the interaction between molecule and accumulation, effectively suppress organic iridium metal complex crystallinity, improve organic iridium metal complex solvability and film forming properties;
3. simultaneously due to alkoxyl group or/and aromatic group introducing, add the three-dimensional space steric effect of this organic iridium metal complex, effectively reduce the interatomic direct effect of iridium metals, thus significantly reduce the self-quenching phenomenon of triplet exciton.
Therefore, in order to make organic iridium metal complex in above-described embodiment, there is more excellent three-dimensional space steric effect, as the preferred embodiments of the present invention, this organic iridium metal complex is preferably organic iridium metal complex of above-mentioned I 3 to I 7, be more preferably organic iridium metal complex that molecular structural formula is I 7, namely said structure leads to the R in organic iridium metal complex of formula I 1, R 2, R 3what three groups were identical or not identical is that alkoxyl group is or/and aromatic group.
In further preferred embodiment, when what Ra, Rb, Rc in this above-mentioned I 1 to I 7 molecular structural formula were identical or not identical is alkoxyl group, this alkoxyl group is C 1~ C 20straight or branched alkoxy base.In a particular embodiment, be also the preferred embodiment of the invention, the alkoxy base in the various embodiments described above is methoxyl group (-OCH 3), hexyloxy (-OC 6h 13), NSC 62789 oxygen base etc.; When what Ra, Rb, Rc in this above-mentioned I 1 to I 7 molecular structural formula were identical or not identical is aromatic group, this aromatic group is the one, two or three in phenyl, fluorenyl, carbazyl.Certainly, one of Ra, Rb, Rc in above-mentioned I 1 to I 7 molecular structural formula or two can be alkoxyl group, remaining two or one is aromatic group.
Thus, organic iridium metal complex of above-mentioned general formula of molecular structure (I) is cyclic metal complexes agent structure with 2-(3'-cyano group-4'-fluorophenyl) pyrimidine, and with 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole is assistant ligand, gives the high blue light color purity of this organic iridium metal complex and luminous efficiency.Wherein, pyrimidine group on 2-(3'-cyano group-4'-fluorophenyl) the main part of pyrimidine is conducive to the lumo energy improving this organic iridium metal complex, on phenyl ring, two strong electron-withdrawing group F bases and cyano group are conducive to the HOMO energy level reducing this organic iridium metal complex, make the effective blue shift of material emission wavelength, the concrete organic iridium metal complex utilizing emitted light spectrogram as Examples below 1 preparation; At least one alkoxyl group on pyrimidine ring is or/and the introducing of aromatic group, the electro mass-energy of giving of this two classes group obtains satisfied blue light emitting wavelength on the one hand, this aromatic group aromatic group of the alkoxyl group and large volume that have carbochain on the one hand in addition can produce larger space steric effect, thus the direct effect between atoms metal can be stoped, significantly reduce the self-quenching phenomenon of triplet exciton; In addition, by the selection to alkoxyl group, aryl substituent group, the space steric effect of this organic iridium metal complex and luminous efficiency and solvent borne and film-forming properties can be improved further.Therefore, on phenyl ring, the introducing of strong electron-withdrawing group fluorine-based, the cyano group of group and high field intensity assistant ligand 3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole can also improve luminescent properties, is beneficial to evaporation, increases film-forming type and improves the stability of device.
Correspondingly, the embodiment of the present invention additionally provides the method that one may be used for the organic iridium metal complex preparing above-mentioned general formula of molecular structure (I), and its preparation method flow process as shown in Figure 1.This organic iridium metal complex preparation method comprises the steps:
S01., the compd A of following structural formula general formula is provided;
S02. compd A is utilized to prepare chlorine bridge dipolymer B: in the environment of anaerobic, the compd A provided in step S01 and hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium are carried out thermal backflow reaction in reaction solvent, generate the chlorine bridge dipolymer B of following structural formula general formula:
S03. by chlorine bridge dipolymer B and 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole carries out organic iridium metal complex that ligand exchange reaction prepares general formula of molecular structure (I): in the environment of anaerobic, by the chlorine bridge dipolymer B for preparing in step S02 and 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole carries out thermal backflow reaction (i.e. ligand exchange reaction) under sodium methylate and/or sodium ethylate catalyst action and in reaction solvent, purifying, obtains organic iridium metal complex of following general formula of molecular structure (I):
Particularly, in above-mentioned steps S01, the R in compd A molecular structural formula 1, R 2, R 3in at least one group be that alkoxyl group is or/and aromatic group.Due to the ring master metal ligand structure that compd A is the organic iridium metal complex of above-described embodiment.Therefore, compd A at least has 7 kinds of structural formulas of (I 1) to (I 7) be similar to as organic iridium metal complex of above-mentioned general formula of molecular structure (I), in order to save length, does not repeat them here.
As preferred embodiment, above-claimed cpd A can be prepared as follows:
In anaerobic, alkaline environment and organo-metallic palladium catalyst, under organic solvent existent condition, the Compound C of following structural formula general formula and 3-cyano group-4-fluorobenzoic boric acid are carried out purifying after Suzuki linked reaction,
Particularly, to carry out the chemical equation of Suzuki linked reaction as follows for this Compound C and 3-cyano group-4-fluorobenzoic boric acid:
Wherein, the R in Compound C 1, R 2, R 3in at least one group be alkoxyl group or/and aromatic group, it can be directly commercial or be prepared acquisition according to vitochemical ultimate principle.
In this Suzuki linked reaction, the condition of this Suzuki coupled reaction can directly be arranged according to the condition of the Suzuki coupled reaction of existing routine.In order to improve the Suzuki coupled reaction speed between Compound Compound C and 3-cyano group-4-fluorobenzoic boric acid, improve the productive rate of compd A, in a preferred embodiment, the condition setting of this Suzuki coupled reaction is: temperature is 85 ~ 100 DEG C, and the reaction times is 10 ~ 15 hours.
In addition, the consumption of the reactant compound C in this Suzuki linked reaction and 3-cyano group-4-fluorobenzoic boric acid can directly add according to ratio in both chemical equation.In order to impel the Suzuki coupled reaction speed between Compound C and 3-cyano group-4-fluorobenzoic boric acid, improve the productive rate of compd A, in a preferred embodiment, the mol ratio of reactant compound C and 3-cyano group-4-fluorobenzoic boric acid consumption is 1:(1 ~ 1.5).In another preferred embodiment, the concentration of this Compound C in reaction solvent is 0.1 ~ 0.2mol/L, is preferably 0.11 ~ 0.14 mol/L.In a particular embodiment, this reaction solvent can select the solvent that Suzuki coupled reaction is conventional, in a preferred embodiment, this reaction solvent is the mixed solvent of volume ratio close to 2:1 of organic solvent and water, wherein, this organic solvent can be dimethyl formamide (DMF), toluene etc.
Organo-metallic palladium catalyst in this Suzuki linked reaction, in further preferred embodiment, this organic palladium catalyzer is tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, at least one of three (dibenzalacetone) two in palladium.In another preferred embodiment, the mole dosage of this organo-metallic palladium catalyst and 2 ~ 6% of Compound C mole dosage, is preferably 4 ~ 6%.
As further preferred embodiment, this organo-metallic palladium catalyst is tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, at least one of three (dibenzalacetone) two in palladium, and 2 ~ 6% of the mole dosage of organo-metallic palladium catalyst and Compound C mole dosage.
As in another preferred embodiment, the condition setting of this Suzuki coupled reaction is: temperature is 85 ~ 100 DEG C, and the reaction times is 6 ~ 12 hours, the mole dosage of organo-metallic palladium catalyst and 2 ~ 6% of Compound C mole dosage.
Above-mentioned each preferred embodiment can improve Suzuki coupled reaction speed further, improves the productive rate of compd A simultaneously.
Alkaline environment in this Suzuki linked reaction ensure that carrying out smoothly of Suzuki linked reaction, and wherein, alkaline environment can be provided, as Cs by the basic cpd that Suzuki linked reaction is conventional 2cO 3, K 2cO 3, Na 2cO 3in one or more mixture, its addition is 1 ~ 3 times of Compound C mole dosage, preferably 1.5 ~ 2.5 times.
Purification process through Suzuki linked reaction products therefrom can operate according to the method for Examples below 1.
In above-mentioned steps S02, hydrated iridium trichloride can be expressed as IrCl 3xH 2o, hydration chlorine sub-iridium acid sodium can be expressed as Na 3irCl 6xH 2o, wherein, x value is preferably 1 ~ 3.Therefore, IrCl 3xH 2o can be IrCl 33H 2o, Na 3irCl 6xH 2o can be Na 3irCl 63H 2o.Certainly, x can also be other values, and like this, hydrated iridium trichloride, hydration chlorine sub-iridium acid sodium also can also be other hydrates.
The temperature of the thermal backflow reaction in this step S02 is determined according to the boiling nature of selected reaction solvent.And this reaction solvent is preferably the mixture of 2-methyl cellosolve, cellosolvo, methylene dichloride, trichloromethane at least one or 2-methyl cellosolve, cellosolvo, methylene dichloride, trichloromethane at least one and distilled water.Be more preferably the mixture of cellosolvo and distilled water.Therefore, the temperature that in this step S02, thermal backflow is reacted is preferably the temperature during thermal backflow of this preferred reaction solvent, and at this preferred thermal backflow temperature, the time of thermal backflow reaction is preferably 20 ~ 30 hours.Certainly, this reaction solvent also can select other alcohol derivate solvent, can also select other organic solvents, therefore, temperature, the time of this step thermal backflow reaction can also be other temperature, time, and when temperature is relatively low, the thermal backflow time can correspondingly extend.
Oxygen-free environment in this step S02 can be vacuum or be full of rare gas element to realize.Realize oxygen-free environment more easily realize owing to being full of rare gas element, therefore, be preferably full of rare gas element to realize oxygen-free environment, this rare gas element is the conventional rare gas element of the art, such as argon gas etc.This oxygen-free environment ensure that the stable of reactant, improves the yield of chlorine bridge dipolymer B.
The chemical equation that compd A in this step S02 and hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium react through thermal backflow is as follows:
Therefore, in above-mentioned steps S02, compd A is 2:1 with the mole dosage ratio of hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium theory, therefore, in order to allow hydrated iridium trichloride or the abundant complete reaction of the sub-iridium acid sodium of hydration chlorine, then compd A is preferably >=2:1 with the mole dosage ratio of iridous chloride or hydration chlorine sub-iridium acid sodium, is preferably (2 ~ 4): 1.Wherein, the concentration range of this iridic compound in reaction solvent is preferably 0.1 ~ 0.2mmol/L.Certainly, compd A also can be allowed fully to react, therefore, compd A is preferably≤2:1 with the mole dosage ratio of hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium.
After the thermal backflow cyclization of step S02, reacted product carried out filter, after purifying and drying treatment, obtain pure compd B.The method of this purifying can be undertaken by the purification process of Examples below 1.
Because the compd B of preparation contains compd A cyclic metal complexes agent structure, again because compd A at least exists 7 kinds of structural formulas mentioned above, therefore compd B equally at least has the 7 kinds of structural formulas be similar to as this compd A, in order to save length, does not repeat them here.
In above-mentioned steps S03, the temperature preferably 40 ~ 84 DEG C that chlorine bridge dipolymer B and 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole thermal backflow are reacted, therefore, this reaction solvent is preferably at least one in ethylene dichloride, methylene dichloride, trichloromethane.Therefore, the temperature that in this step S03, thermal backflow is reacted is preferably the temperature during thermal backflow of this preferred reaction solvent, and as in a particular embodiment, when trichloromethane selected by back flow reaction solvent, the temperature of this thermal backflow reaction can be set to 62 DEG C.The time of thermal backflow reaction is relevant with the temperature of thermal response, and in order to make reactant fully react, time as relatively low in temperature, the thermal backflow time can correspondingly extend.In a preferred embodiment, at this preferred thermal backflow temperature, the time of thermal backflow reaction is preferably 8 ~ 20 hours.In a particular embodiment, when trichloromethane selected by back flow reaction solvent, the temperature of this thermal backflow reaction is set to 62 DEG C, and the thermal backflow time is 12 hours.
The chemical equation that chlorine bridge dipolymer B in this step S03 and 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole heat are reacted through thermal backflow is as follows:
Therefore, 3-trifluoromethyl-5-(2'-pyridyl)-1 in above-mentioned steps S03,2,4-triazole is 2:1 with the mole dosage ratio of compd B theory, in order to make the abundant complete reaction of compd B, 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole is preferably >=2:1 with the mole dosage ratio of compd B, is preferably (2 ~ 4): 1.Wherein, the concentration of compd B in reaction solvent is preferably 0.01 ~ 0.02mol/L.
In addition, in order to improve the efficiency of thermal backflow reaction in this step S03, improve the yield of target product, in a preferred embodiment, sodium methylate and/or sodium ethylate catalyzer are (8 ~ 12) with the mole dosage ratio of chlorine bridge dipolymer B: 1.
In further preferred embodiment, sodium methylate and/or sodium ethylate catalyzer are (8 ~ 12) with the mole dosage ratio of chlorine bridge dipolymer B: 1,3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole is (3 ~ 2) with the mole dosage ratio of chlorine bridge dipolymer B: 1.
Oxygen-free environment in this step S03 can be vacuum or be full of rare gas element to realize.Realize oxygen-free environment more easily realize owing to being full of rare gas element, therefore, be preferably full of rare gas element to realize oxygen-free environment, this rare gas element is the conventional rare gas element of the art, such as argon gas etc.This oxygen-free environment ensure that the stable of reactant, improves the yield of reaction product.
After the thermal backflow cyclization of step S03, reacted product carried out filter, after purifying and drying treatment, obtain organic iridium metal complex of pure general formula of molecular structure (I).The method of this purifying can be carried out according to the purification process of Examples below 1.
Reactant only need be carried out thermal backflow and react by above-mentioned organic iridium metal complex preparation method, and the one-tenth ripening reaction only needing 2-3 to walk is without the need to special equipment and environmental requirement, and its preparation method technique is simple, productive rate is high, and mild condition, be easy to operate and control, be suitable for suitability for industrialized production.
Have as above-mentioned high blue light color purity and luminous efficiency just because of the organic iridium metal complex of above-described embodiment, and by the group in cyclic metal complexes agent structure if alkoxyl group, aromatic group are to the adjustment of emission wavelength, its solubleness, good film-forming property, self-quenching phenomenon incidence is low, there is charge transport properties simultaneously good, therefore, this organic iridium metal complex can as the application of blue electrophosphorescence material in organic electroluminescence device, EL cold light film or electrochemical cell luminescent device.In application process, can using organic for embodiment of the present invention iridium metal complex as luminescent layer or with other luminescent material compound uses, prepare and there is stable luminescence, and the electroluminescent device that luminous efficiency is high.
Particularly, when the organic iridium metal complex of above-described embodiment as blue electrophosphorescence at organic electroluminescence device (organic electroluminescent LED, during application OLED), this organic electroluminescence device comprises substrate layer, the first electrode layer, organic function layer and the second electrode lay.Wherein, organic function layer comprises the hole transmission layer of stacked setting, at least one luminescent layer and electron transfer layer, and the luminescent material of this luminescent layer contains the organic iridium metal complex of above-described embodiment.
Certainly, the organic function layer of this organic electroluminescence device can also comprise the functional layers such as hole injection layer, electron injecting layer, hole blocking layer, electronic barrier layer, and this functional layer is conveniently stacked to be arranged.Containing the organic iridium metal complex of above-described embodiment in the luminescent layer of this organic electroluminescence device, the material selection material known in this field of other each Rotating fields, its preparation method also can according to the existing method preparation in this area.
Particularly, when the organic iridium metal complex of above-described embodiment is as the application of blue electrophosphorescence material in electrochemical cell luminescent device, this electrochemical cell luminescent device comprises anode, negative electrode and is arranged at least one luminescent layer between this anode, negative electrode, and the luminescent material of this luminescent layer contains the organic iridium metal complex of above-described embodiment.Wherein, containing the organic iridium metal complex of above-described embodiment in the luminescent layer of this electrochemical cell luminescent device, the material selection material known in this field of anode, negative electrode, its preparation method also can according to the existing method preparation in this area.
Now in conjunction with the embodiments, the present invention is further elaborated.
Embodiment 1
Two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-phenyl pyrimidine-N, C 2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close iridium metal complex and synthetic method thereof:
(1) the synthesis synthesis of 2-(3'-cyano group-4'-fluorophenyl)-5-phenyl pyrimidine:
Under nitrogen protection, the bromo-5-phenyl pyrimidine of 2.35g (10mmol) 2-, 1.65g (12mmol) 3-cyano group-4-fluorobenzoic boric acid and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 50mL toluene, drip the aqueous solution of 25mL containing 2.76g (20mmol) salt of wormwood subsequently in reaction system; Be heated to stirring reaction 10h under 100 DEG C of state of temperatures; After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying; Filter, filtrate decompression steams solvent and obtains crude product; With volume ratio be 1/3 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 1.29g, yield is 46.9%; Its chemical equation is as follows:
2-(3'-cyano group-4'-fluorophenyl)-5-phenyl pyrimidine product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 275.1 (M +); Ultimate analysis: C17H10FN3; Theoretical value: C, 74.17; H, 3.66; F, 6.90; N, 15.26; Measured value: C, C, 74.12; H, 3.73; F, 6.86; N, 15.29.The material that the above-mentioned reaction of this data acknowledgement obtains is 2-(3'-cyano group-4'-fluorophenyl)-5-phenyl pyrimidine.
(2) part be 2-(3'-cyano group-4'-fluorophenyl)-5-phenyl pyrimidine containing the dimeric synthesis of iridium dichloro:
Under nitrogen protection, 0.35g (1mmol) three hydrated iridium trichloride, it is in the cellosolvo/water mixed liquid of 3:1 that 0.69g (2.5mmol) 2-(3'-cyano group-4'-fluorophenyl)-5-phenyl pyrimidine is dissolved in 30mL volume ratio, is heated to stirring reaction 24h under reflux state; After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter; Solid uses distilled water, methanol wash successively, and obtain solids 0.39g after drying, yield is 50.2%; Dipolymer, without the need to further purification, can directly drop in next step reaction; Its chemical equation is as follows:
Two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-phenyl pyrimidine-N, C 2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close the synthesis of iridium metal complex:
Under nitrogen protection, 0.78g (0.5mmol) main part be 2-(3'-cyano group-4'-fluorophenyl)-5-phenyl pyrimidine containing iridium dichloro dimer and 0.27g (1.25mmol) 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole is dissolved in 15mL1, in 2-ethylene dichloride, drip 1, the 2-dichloroethane solution of 10mL containing 0.27g (5mmol) sodium methylate subsequently, stirring heating is warming up to reflux state reaction 8h; Naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out; Filter, collect crude product, solid uses deionized water, methanol wash for several times successively, and obtain 0.38g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 39.8%; Its chemical equation is as follows:
Product is carried out the result of Structural Identification: mass spectrum (MS m/z): 954.2 (M +); Ultimate analysis: C42H22F5IrN10; Theoretical value: C, 52.88; H, 2.32; F, 9.96; Ir, 20.15; N, 14.68; Measured value: C, 52.83; H, 2.39; F, 9.93; Ir, 20.19; N, 14.66.The material that the above-mentioned reaction of this data acknowledgement obtains is two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-phenyl pyrimidine-N, C 2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close iridium metal complex.
Embodiment 2
Two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4-(fluorenes-9 '-Ji) pyrimidine-N, C 2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close iridium metal complex and synthetic method thereof:
(1) 2-(3'-cyano group-4'-fluorophenyl)-4-(Wu ?9 ’ ?base) synthesis of pyrimidine:
Under nitrogen protection, the bromo-4-of 3.23g (10mmol) 2-(fluorenes-9 '-Ji) pyrimidine, 1.65g (10mmol) 3-cyano group-4-fluorobenzoic boric acid and the two chlorine two (triphenyl phosphorus) of 0.42g (0.6mmol) are closed palladium and are dissolved in 60mL N, in dinethylformamide, in reaction system, drip the aqueous solution of 30mL containing 1.59g (15mmol) sodium carbonate subsequently; Be heated to stirring reaction 12h under 90 DEG C of states; After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying; Filter, filtrate decompression steams solvent and obtains crude product; With volume ratio be 1/1 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 1.21 g, yield is 33.3%; Its chemical equation is as follows:
Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 363.1 (M +); Ultimate analysis: C24H14FN3; Theoretical value: C, 79.33; H, 3.88; F, 5.23; N, 11.56; Measured value: C, 79.27; H, 3.93; F, 5.26; N, 11.54.The material that the above-mentioned reaction of this data acknowledgement obtains is 2-(3'-cyano group-4'-fluorophenyl)-4-(fluorenes-9 '-Ji) pyrimidine.
(2) part be 2-(3'-cyano group-4'-fluorophenyl)-4-(fluorenes-9 '-Ji) pyrimidine containing the dimeric synthesis of iridium dichloro:
Under nitrogen protection, 0.35g (1mmol) three hydrated iridium trichloride and 1.09g (3mmol) 2-(3'-cyano group-4'-fluorophenyl)-4-(fluorenes-9 '-Ji) pyrimidine is dissolved in 40mL2-ethoxy ethanol/water (3/1) mixed solution, stirring reaction 24h at reflux; After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter.Solid uses distilled water, methanol wash successively, and obtain solids 0.35g after drying, yield is 37.9%; Dipolymer, without the need to further purification, can directly drop in next step reaction; Its chemical equation is as follows:
(3) two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4-(fluorenes-9 '-Ji) pyrimidine-N, C 2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close the synthesis of iridium metal complex:
Under nitrogen protection, 0.76g (0.4mmol) main part be 2-(3'-cyano group-4'-fluorophenyl)-4-(fluorenes-9 '-Ji) pyrimidine containing iridium dichloro dimer and 0.17g (0.8mmol) 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole is dissolved in 15mL methylene dichloride, drip the dichloromethane solution of 10mL containing 0.22g (3.2mmol) sodium ethylate subsequently, stirring heating is warming up to 40 DEG C of reflux state reaction 20h; Naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out; Filter, collect crude product, solid uses deionized water, methanol wash for several times successively, and obtain 0.19g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 21.0%; Its chemical equation is as follows:
Product is carried out the result of Structural Identification: mass spectrum (MS m/z): 1130.2 (M +); Ultimate analysis: C56H30F5IrN10; Theoretical value: C, 59.52; H, 2.68; F, 8.41; Ir, 17.01; N, 12.39; Measured value: C, 59.48; H, 2.62; F, 8.53; Ir, 17.04; N, 12.33.The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(the fluoro-5'-cyano-phenyl of 4'-)-4-(fluorenes-9 '-Ji) pyrimidine-N, C 2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close iridium metal complex.
Embodiment 3
Two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-(carbazole-N-base) pyrimidine-N, C 2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close iridium metal complex and synthetic method thereof:
(1) synthesis of 2-(3'-cyano group-4'-fluorophenyl)-5-(carbazole-N-base) pyrimidine:
Under nitrogen protection; the bromo-5-of 1.62g (5mmol) 2-(carbazole-N-base) pyrimidine, 1.24g (7.5mmol) 3-cyano group-4-fluorobenzoic boric acid and 0.23g (0.2mmol) four (triphenyl phosphorus) close palladium and are dissolved in 24mL toluene, drip the aqueous solution of 12mL containing 1.73g (12.5mmol) salt of wormwood subsequently in reaction system.Be heated to stirring reaction 15h under 85 DEG C of state of temperatures.After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying.Filter, filtrate decompression steams solvent and obtains crude product.With volume ratio be 1/1 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 0.64g, yield is 35.1%; Its chemical equation is as follows:
Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 364.1 (M +); Ultimate analysis: C23H13FN4; Theoretical value: C, 75.81; H, 3.60; F, 5.21; N, 15.38; Measured value: C, 75.84; H, 3.55; F, 5.27; N, 15.34.The material that the above-mentioned reaction of above data acknowledgement obtains is 2-(3'-cyano group-4'-fluorophenyl)-5-(carbazole-N-base) pyrimidine.
(2) part be 2-(3'-cyano group-4'-fluorophenyl)-5-(carbazole-N-base) pyrimidine containing the dimeric synthesis of iridium dichloro:
Under nitrogen protection, the Na of 1mmol 3irCl 63H 2o, 0.73g (2mmol) 2-(3'-cyano group-4'-fluorophenyl)-5-(carbazole-N-base) pyrimidine is dissolved in 50mL2-ethoxy ethanol/water (3/1) mixed solution, stirring reaction 24h at reflux; After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter; Solid uses distilled water, methanol wash successively, and obtain solids 0.38g after drying, yield is 39.8%; Dipolymer, without the need to further purification, can directly drop in next step reaction; Its chemical equation is as follows:
(3) two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-(carbazole-N-base) pyrimidine-N, C 2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close the synthesis of iridium metal complex:
Under nitrogen protection, 0.57g (0.3mmol) main part be 2-(3'-cyano group-4'-fluorophenyl)-5-(carbazole-N-base) pyrimidine containing iridium dichloro dimer and 0.19g (0.9mmol) 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole is dissolved in 20mL trichloromethane, drip the chloroform soln of 10mL containing 0.19g (3.6mmol) sodium ethylate subsequently, stirring heating is warming up to 62 DEG C of reflux state reaction 15h; Naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out; Filter, collect crude product, solid uses deionized water, methanol wash for several times successively, and obtain 0.15g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 22.1%; Its chemical equation is as follows:
Product is carried out the result of Structural Identification: mass spectrum (MS m/z): 1132.2 (M +); Ultimate analysis: C54H28F5IrN12; Theoretical value: C, 57.29; H, 2.49; F, 8.39; Ir, 16.98; N, 14.85; Measured value: C, 57.24; H, 2.55; F, 8.33; Ir, 16.96; N, 14.92.The material that the above-mentioned reaction of above data acknowledgement obtains is two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-(carbazole-N-base) pyrimidine-N, C 2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close iridium close iridium metal complex.
Embodiment 4
Two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-methoxy pyrimidine-N, C 2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close iridium metal complex and synthetic method thereof:
(1) the synthesis synthesis of 2-(3'-cyano group-4'-fluorophenyl)-5-methoxy pyrimidine:
Under nitrogen protection, the bromo-5-methoxy pyrimidine of 1.89g (10mmol) 2-, 1.65g (12mmol) 3-cyano group-4-fluorobenzoic boric acid and 0.58g (0.5mmol) four (triphenyl phosphorus) close palladium and are dissolved in 35mL DMF, drip the aqueous solution of 15mL containing 2.76g (20mmol) salt of wormwood subsequently in reaction system; Be heated to stirring reaction 6h under 100 DEG C of state of temperatures; After question response liquid cooling to room temperature, dichloromethane extraction, separatory, be washed to neutrality, anhydrous magnesium sulfate drying; Filter, filtrate decompression steams solvent and obtains crude product; With volume ratio be 1/7 ethyl acetate be separated for elutriant carries out silica gel column chromatography with normal hexane, after drying solid 1.14g, yield is 49.7%; Its chemical equation is as follows:
Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 229.1 (M +); Ultimate analysis: C12H8FN3O; Theoretical value: C, 62.88; H, 3.52; F, 8.29; N, 18.33; O, 6.98; Measured value: C, 62.84; H, 3.57; F, 8.25; N, 18.38; O, 6.96.The material that the above-mentioned reaction of this data acknowledgement obtains is 2-(3'-cyano group-4'-fluorophenyl)-5-methoxy pyrimidine.
(2) part be 2-(3'-cyano group-4'-fluorophenyl)-5-methoxy pyrimidine containing the dimeric synthesis of iridium dichloro:
Under nitrogen protection, 0.36g (1mmol) three hydrated iridium trichloride, it is in the cellosolvo/water mixed liquid of 3:1 that 0.46g (2mmol) 2-(3'-cyano group-4'-fluorophenyl)-5-methoxy pyrimidine is dissolved in 20mL volume ratio, is heated to stirring reaction 24h under reflux state; After being chilled to room temperature, rotating and steam except partial solvent, add appropriate distilled water, filter; Solid uses distilled water, methanol wash successively, and obtain solids 0.33g after drying, yield is 48.2%; Dipolymer, without the need to further purification, can directly drop in next step reaction; Its chemical equation is as follows:
(3) two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-methoxy pyrimidine-N, C 2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close the synthesis of iridium metal complex:
Under nitrogen protection, 0.68g (0.5mmol) main part be 2-(3'-cyano group-4'-fluorophenyl)-5-methoxy pyrimidine containing iridium dichloro dimer and 0.27g (1.25mmol) 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole is dissolved in 15mL1, in 2-ethylene dichloride, drip 1, the 2-dichloroethane solution of 10mL containing 0.27g (5mmol) sodium methylate subsequently, stirring heating is warming up to reflux state reaction 8h; Naturally after being chilled to room temperature, concentrated remove portion solvent, the appropriate distilled water of impouring, has solid to separate out; Filter, collect crude product, solid uses deionized water, methanol wash for several times successively, and obtain 0.38g pure products through methylene dichloride and dehydrated alcohol mixed solvent recrystallization, yield is 44.1%; Its chemical equation is as follows:
Product is carried out the result of Structural Identification:
Mass spectrum (MS m/z): 862.1 (M +); Ultimate analysis: C32H18F5IrN10O2; Theoretical value: C, 44.60; H, 2.11; F, 11.02; Ir, 22.31; N, 16.25; O, 3.71; Measured value: C, 44.66; H, 2.04; F, 11.08; Ir, 22.26; N, 16.23; O, 3.73.The material that the above-mentioned reaction of this data acknowledgement obtains is two (2-(the fluoro-5'-cyano-phenyl of 4'-)-5-methoxy pyrimidine-N, C 2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close iridium metal complex.
Comparison example 1
Direct acquisition organic electromechanical phosphorescent material two [2-(4', 6'-difluorophenyl) pyridine-N, C 2'] (2-pyridinecarboxylic) close iridium (FIrpic), plays structure as follows:
Performance test:
Existing organic iridium metal complex FIrpic in organic iridium metal complex of above-described embodiment 1 ~ 4 preparation and comparison example 1 is carried out spectroscopic analysis and luminous quantum efficiency mensuration, testing method is as follows:
Spectroscopic analysis: the organic iridium metal complex prepared by above-described embodiment 1 ~ 4 respectively compound concentration is 10 -6the CH of M 2c l2solution, then carries out emmission spectrometric analysis respectively at 298K temperature.
Luminous quantum efficiency measure: by above-described embodiment 1 ~ 4 prepare organic iridium metal complex and comparison example 1 in existing organic iridium metal complex FIrpic respectively compound concentration be 10 -6the CH of M 2c l2solution, then carries out luminous quantum efficiency mensuration.
The result that emmission spectrometric analysis and luminous quantum efficiency record is as following table 1:
Table 1
Wherein, organic iridium metal complex prepared by above-described embodiment 1 ~ 4 is carrying out in emmission spectrometric analysis respectively, organic iridium metal complex in embodiment 1 has an acromion at 484nm place simultaneously, organic iridium metal complex in embodiment 2 has an acromion at 494nm place simultaneously, organic iridium metal complex in embodiment 3 has an acromion at 492nm place simultaneously, organic iridium metal complex in embodiment 4 has an acromion at 486nm place simultaneously.In addition, as shown in Figure 2, in Fig. 2, transverse axis is emission wavelength (unit nm) to the emmission spectrum of organic iridium metal complex prepared by embodiment 1, and the longitudinal axis is the photoluminescence intensity (a.u.) after normalization method.
Can be found out by table 1 and Fig. 2, organic iridium metal complex that the organic iridium metal complex of the embodiment of the present invention is prepared as above-described embodiment 1 ~ 3 is compared with existing organic iridium metal complex, its blue light purity of launching is high, there is higher luminous quantum efficiency, its luminous efficiency is high, therefore, can be used as blue light electroluminescent material to be widely used in technical field of organic electroluminescence.
Application Example 1
Containing organic iridium metal complex organic electroluminescence device (OLED) prepared by embodiment 1 and preparation method thereof:
As shown in Figure 3, it comprises the glass substrate 1, anode layer 2, hole injection layer 31, hole transmission layer 32, electronic barrier layer 33, luminescent layer 34, hole blocking layer 35, electron transfer layer 36, electron injection buffer layer 37 and the cathode layer 4 that stack gradually combination to the structure of this OLED.Wherein, hole injection layer 31, hole transmission layer 32, electronic barrier layer 33, luminescent layer 34, hole blocking layer 35, electron transfer layer 36, electron injection buffer layer 37 form organic function layer 3, two (2-(4'-cyano group-5'-fluorophenyl)-5-phenyl pyrimidine-N, C prepared by the embodiment 1 containing 7wt% in this luminescent layer 34 2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles) close iridium metal complex.Its concrete structure the following is Ir title complex (30nm)/BCP (10nm)/Alq3 (35nm)/LiF (1nm)/Al (120nm) prepared by glass/ITO (100nm)/m-MTDATA (40nm)/NPB (20nm)/mCP (10nm)/mCP:7wt% embodiment 1.
This OLED preparation method is as follows: a glass substrate 1 depositing a layer thickness is 200nm, square resistance is that the tin indium oxide (ITO) of 10 ~ 20 Ω/mouth is as transparent anode 2, on anode 301, the m-MTDATA(4 that a layer thickness is 40nm is prepared successively by vacuum evaporation, 4', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine) hole-injecting material is as hole injection layer 31, a layer thickness is the NPB(N of 20nm, two (1-the naphthyl)-N of N'-, N'-diphenylbenzidine) hole mobile material is as hole transmission layer 32, a layer thickness is the mCP(1 of 10nm, two (9-carbazyl) benzene of 3-) electron-blocking materials is two (2-(4'-cyano group-5'-the fluorophenyl)-5-phenyl pyrimidine-N prepared doped with 7wt% embodiment 1 of 30nm as electronic barrier layer 33 and a layer thickness, C 2') (3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole) close the mCP of iridium as luminescent layer 34, on this luminescent layer 34, vacuum evaporation a layer thickness is successively the BCP(2 of 10nm again, 9-dimethyl-4,7-phenylbenzene-phenanthrolene) material be the Alq3 (three (oxine) aluminium) of 35nm as hole blocking layer 35, thickness is that the LiF of 1nm is as electron injection buffer layer 37 as electron transfer layer 36, thickness, the last vacuum plating of employing on the buffer layer techniques of deposition thickness is the metal A l of 120nm, as the negative electrode 4 of device.
Know through performance test, the maximum emission wavelength of the electroluminescent spectrum of this device is positioned at 462nm, has an acromion at 486nm place, and the maximum current efficiency of device is 8.7cd/A, and maximum external quantum efficiency is 4.7%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. an organic iridium metal complex, its general formula of molecular structure is following (I):
In formula, R 1, R 2, R 3at least one group during identical or not identical is is that alkoxyl group is or/and aromatic group.
2. organic iridium metal complex according to claim 1, is characterized in that: described aromatic group is at least one in phenyl, fluorenyl, carbazyl.
3. organic iridium metal complex according to claim 1 and 2, is characterized in that: described alkoxyl group is C 1~ C 20straight or branched alkoxyl group.
4. a preparation method for organic iridium metal complex, comprises the steps:
The compd A of following structural formula general formula is provided:
In the environment of anaerobic, described compd A and hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium are carried out thermal backflow reaction in reaction solvent, generate the chlorine bridge dipolymer B of following structural formula general formula:
In the environment of anaerobic, by described chlorine bridge dipolymer B and 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole is under sodium methylate and/or sodium ethylate catalyst action and carry out thermal backflow reaction in reaction solvent, purifying, obtains organic iridium metal complex of following general formula of molecular structure (I):
Wherein, the R in compd A, B and general structure (I) 1, R 2, R 3in at least one group be that alkoxyl group is or/and aromatic group.
5. the preparation method of organic iridium metal complex according to claim 4, it is characterized in that: in the step that compd A and hydrated iridium trichloride or the thermal backflow of hydration chlorine sub-iridium acid sodium reacts, the mole dosage of described compd A and hydrated iridium trichloride or hydration chlorine sub-iridium acid sodium is than being (2 ~ 4): 1.
6. the preparation method of organic iridium metal complex according to claim 4, it is characterized in that: at described chlorine bridge dipolymer B and 3-trifluoromethyl-5-(2'-pyridyl)-1,2, in the step of 4-triazole thermal backflow reaction, described catalyzer is (8 ~ 12) with the mole dosage ratio of chlorine bridge dipolymer B: 1; And/or described 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazoles are (3 ~ 2) with the mole dosage ratio of chlorine bridge dipolymer B: 1.
7. the preparation method of the organic iridium metal complex according to any one of claim 4 ~ 6, it is characterized in that: in the step that described compd A and hydrated iridium trichloride or the thermal backflow of hydration chlorine sub-iridium acid sodium react, described reaction solvent is the mixture of 2-methyl cellosolve, cellosolvo, methylene dichloride, trichloromethane at least one or 2-methyl cellosolve, cellosolvo, methylene dichloride, trichloromethane at least one and distilled water; And/or,
In the step that described chlorine bridge dipolymer B and 3-trifluoromethyl-5-(2'-pyridyl)-1,2,4-triazole thermal backflow are reacted, described reaction solvent is at least one in 1.2 ethylene dichloride, methylene dichloride, trichloromethane.
8. the preparation method of the organic iridium metal complex according to any one of claim 4 ~ 6, is characterized in that, the preparation method of described compd A is as follows:
In anaerobic, alkaline environment and organo-metallic palladium catalyst, under organic solvent existent condition, the Compound C of following structural formula general formula and 3-cyano group-4-fluorobenzoic boric acid are carried out purifying after Suzuki linked reaction,
Wherein, the R in Compound C 1, R 2, R 3in at least one group be that alkoxyl group is or/and aromatic group.
9. the preparation method of organic iridium metal complex according to claim 8, is characterized in that: the temperature of described Suzuki linked reaction is 85 ~ 100 DEG C, and the time is 6 ~ 12h; And/or,
The mole dosage of described organo-metallic palladium catalyst is 2 ~ 5% of Compound C mole dosage.
10. the organic iridium metal complex as described in as arbitrary in claims 1 to 3 is as the application of blue electrophosphorescence material in organic electroluminescence device, EL cold light film or electrochemical cell luminescent device.
CN201310367782.8A 2013-08-21 2013-08-21 Organic iridium metal complex and preparation method and application thereof Pending CN104418899A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310367782.8A CN104418899A (en) 2013-08-21 2013-08-21 Organic iridium metal complex and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310367782.8A CN104418899A (en) 2013-08-21 2013-08-21 Organic iridium metal complex and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN104418899A true CN104418899A (en) 2015-03-18

Family

ID=52969090

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310367782.8A Pending CN104418899A (en) 2013-08-21 2013-08-21 Organic iridium metal complex and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN104418899A (en)

Similar Documents

Publication Publication Date Title
CN104342117A (en) Organic electro-phosphorescent material and preparation method thereof, and organic electroluminescent device
CN104418899A (en) Organic iridium metal complex and preparation method and application thereof
CN104418896A (en) Organic iridium metal complex and preparation method and application thereof
CN104418904A (en) Organic iridium metal complex and preparation method and application thereof
CN104418895A (en) Organic iridium metal complex and preparation method and application thereof
CN104418898A (en) Organic iridium metal complex and preparation method and application thereof
CN104418894A (en) Organic iridium metal complex and preparation method and application thereof
CN104342112A (en) Organic electro-phosphorescent material and preparation method thereof, and organic electroluminescent device
CN104418905A (en) Organic iridium metal complex and preparation method and application thereof
CN104342115A (en) Organic electrophosphorescent material and preparation method thereof and organic light-emitting device
CN104341454A (en) Organic electro-phosphorescent material and preparation method thereof, and organic electroluminescent device
CN104418918A (en) Organic iridium metal complex and preparation method and application thereof
CN104418902A (en) Organic iridium metal complex and preparation method and application thereof
CN104177410A (en) Blue electrophosphorescent material iridium metal complex, preparation method and organic electroluminescent device
CN104177411A (en) Blue electrophosphorescent material iridium metal complex, preparation method and organic electroluminescent device
CN104418903A (en) Organic iridium metal complex and preparation method and application thereof
CN104418901A (en) Organic iridium metal complex and preparation method and application thereof
CN104177432A (en) Blue-light organic electrophosphorescent materials, preparing method thereof and applications of the materials
CN104418900A (en) Organic iridium metal complex and preparation method and application thereof
CN104418917A (en) Organic iridium metal complex and preparation method and application thereof
CN104418897A (en) Organic iridium metal complex and preparation method and application thereof
CN104177425A (en) Blue light organic electrophosphorescent material iridium metal complex, preparation method thereof, and organic electroluminescent device
CN104418916A (en) Organic iridium metal complex and preparation method and application thereof
CN104119390A (en) Organic iridium metal complex and preparation method and application thereof
CN104342114A (en) Organic electro-phosphorescent material and preparation method thereof, and organic electroluminescent device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20150318