CN104119393A - 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
CN104119393A
CN104119393A CN201310150560.0A CN201310150560A CN104119393A CN 104119393 A CN104119393 A CN 104119393A CN 201310150560 A CN201310150560 A CN 201310150560A CN 104119393 A CN104119393 A CN 104119393A
Authority
CN
China
Prior art keywords
metal complex
iridium metal
methyl
organic
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
CN201310150560.0A
Other languages
Chinese (zh)
Inventor
周明杰
王平
张娟娟
梁禄生
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 CN201310150560.0A priority Critical patent/CN104119393A/en
Publication of CN104119393A publication Critical patent/CN104119393A/en
Pending legal-status Critical Current

Links

Abstract

The invention discloses an organic iridium metal complex and a preparation method and application thereof. The structure of the organic iridium metal complex is shown as the following molecular structural general formula (I), and in the formula (I), R is H or methyl. The preparation method includes the steps of the preparation of a chlorine bridge dimer, and reaction of the chlorine bridge dimer and iridium metal ligand 5-(9'-carbazolyl)-2-substituted phenyl benzotriazole to prepare the organic iridium metal complex shown as the structural general formula (I). The organic iridium metal complex uses the 5-(9'-carbazolyl)-2-substituted phenyl benzotriazole as an iridium metal ligand body structure, so that the organic iridium metal complex can obtain excellent green-yellow light emitting properties, and the organic iridium metal complex used as a luminescence material is conductive to balancing the charge transfer in a device and improving the El (electroluminescence) properties of the device. At the same time, through regulation of the light emitting wavelength of the organic iridium metal complex by a chemical modification group, phosphorescence emission of different green-yellow light emitting wavelengths can be obtained. The organic iridium metal complex is simple and high in yield.

Description

Organic iridium metal complex and its preparation method and application
Technical field
The invention belongs to technical field of organic luminescence materials, relate to specifically a kind of organic iridium metal complex and its preparation method and application.
Background technology
Organic electroluminescent (EL) refers to that organic materials is under electric field action, electric energy is converted into a kind of luminescence phenomenon of luminous energy.Owing to thering is ultra-thin, complete solidify, luminous, fast response time, good temp characteristic, can realize the characteristics such as soft demonstration, have a wide range of applications in various fields.
In organic electroluminescent field, except common are organic electro luminescent diode (Organic light emitting diodes, OLEDs) in addition, also has a kind of electrochemical cell luminescent device (Light emitting electrochemical cells, LECs), its principle is dopant ion compound or use ionic compound to make luminescent layer completely in organic electro luminescent layer.
In early days former because the driving voltage of organic electroluminescence device is too high, luminous efficiency is low etc. thereby make the research of organic electroluminescent stay cool.Until 1987, the human hairs such as the Tang of Kodak understand taking oxine aluminium (Alq3) as luminescent materials luminescent layer, with the high-quality thin film of making even compact with aromatic diamine hole transmission layer, low-work voltage, high brightness, high efficiency organic electroluminescence device (quantum yield 1%, luminous efficiency 1.5lm/W, high brightness >1000cd/m are made 2, driving voltage≤10V), opened the new prelude to electroluminescent organic material research.But due to the restriction of the statistical theory that is subject to spinning, 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 the hot research direction in this field after this.1997, Forrest etc. find electrophosphorescence phenomenon, and the research that mixes up the organic electroluminescent in Alq3 using phosphor material octaethyl leaf beautiful jade platinum (PtOEP) as object luminescent material disclosed, make the internal quantum efficiency of electroluminescent organic material break through 25% restriction, make the research of electroluminescent organic material enter another new period.
Subsequently, be more and more developed for the phosphor material of Organic Light Emitting Diode, their overwhelming majority are all the title complexs of containing element periodictable transition period metal ion.But the title complex of existing metal ion one side is due to the reason of cyclic metal complexes agent structure itself, affect the luminous of phosphor material, on the other hand, between atoms metal in the title complex of metal ion, easily there is direct effect and cause the generation of the self-quenching phenomenon of triplet exciton, thereby had a strong impact on the electroluminescent properties of phosphorescent light-emitting materials.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, a kind of organic iridium metal complex and application preparation method thereof with excellent electroluminescent properties is provided.
Another object of the present invention is to provide a kind of productive rate of above-mentioned organic iridium metal complex high, the preparation method who is easy to operate and control.
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 3, R 4identical or not identical is H or methyl.
And a kind of method of preparing above-mentioned 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 is carried out to thermal backflow with hydration iridous chloride or the sub-iridium acid of hydration chlorine sodium in reaction solvent and react, generate the chlorine bridge dipolymer B of following structural formula general formula;
In the environment of anaerobic, by described chlorine bridge dipolymer B and 2,2,6,6-tetramethyl--3,5-heptadione carries out thermal backflow reaction in reaction solvent, and purifying obtains organic iridium metal complex of described general formula of molecular structure (I);
Wherein, the R in compd A, compd B general molecular formula 1, R 2, R 3, R 4identical or not identical is H or methyl.
And above-mentioned organic iridium metal complex is the application in organic electroluminescence device, EL cold light film or electrochemical cell luminescent device as electroluminescent phosphorescence material.
Above-mentioned organic iridium metal complex is taking 5-(9 '-carbazyl)-2-phenyl benzotriazole as cyclic metal complexes agent structure, and with 2,2,6,6-tetramethyl--3,5-heptadione is assistant ligand, makes this organic iridium metal complex have the performance of excellent jaundice green glow.This 5-(9 '-carbazyl)-2-phenyl benzotriazole agent structure has the benzotriazole group of larger planar rigidity, it is conducive to the luminous of phosphorescence on the one hand, can effectively control on the other hand highest occupied molecular orbital(HOMO) (HOMO) and lowest unocccupied molecular orbital (LUMO) energy level of material, and be conducive to the electric charge transmission in balancing device, thereby improve the electroluminescent properties of device.In the time that methyl group is introduced in the C position on the phenyl ring being connected with azoles nitrogen in cyclic metal complexes agent structure, the existence of this methyl group can realize the adjusting to this organic iridium metal complex emission wavelength, thereby obtains the phosphorescent emissions of different yellow-green colour emission wavelengths.And the existence of this methyl group can also produce space steric effect, reduce the interatomic direct effect of iridium metals, reduce the self-quenching phenomenon of triplet exciton, thereby ensured the electroluminescent intensity of this organic iridium metal complex.
Above-mentioned organic iridium metal complex preparation method is simple, and productive rate is high, and reaction conditions gentleness, is easy to operate and control, and is suitable for suitability for industrialized production.
Brief description of the drawings
Fig. 1 is the organic iridium metal complex preparation method's of the embodiment of the present invention schema;
Fig. 2 be embodiment 1 prepare two [5-(9 '-carbazyl)-2-phenyl-1,2,3-benzotriazole-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex and carry out spectroscopic analysis figure;
Fig. 3 is two [5-(9 '-carbazyl)-2-phenyl-1,2,3-benzotriazole-N, the C that prepare with embodiment 1 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the OLED structural representation 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 clearer, 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, is not intended to limit the present invention.
The invention provides a kind of organic iridium metal complex with excellent electroluminescent intensity and the green glow that can turn to be yellow, its general formula of molecular structure is following (I):
Particularly, the R in (I) formula 1, R 2, R 3, R 4identical or not identical is H or methyl.Therefore, the organic iridium metal complex of this general formula of molecular structure (I) at least has following 15 kinds of molecular structural formulas:
Above-mentioned (I 2) to the R in (I 15) molecular structural formula be methyl.
Organic iridium metal complex of above-mentioned general formula of molecular structure (I) is taking 5-(9 '-carbazyl)-2-phenyl benzotriazole as cyclic metal complexes agent structure, and with 2,2,6,6-tetramethyl--3,5-heptadione is assistant ligand, makes this organic iridium metal complex have the performance of excellent jaundice green glow.This 5-(9 '-carbazyl)-2-phenyl benzotriazole agent structure has the benzotriazole group of larger planar rigidity, it is conducive to the luminous of phosphorescence on the one hand, can effectively control on the other hand highest occupied molecular orbital(HOMO) (HOMO) and lowest unocccupied molecular orbital (LUMO) energy level of material, and be conducive to the electric charge transmission in balancing device, thereby improve the electroluminescent properties of device.In the time that methyl group is introduced in the C position on the phenyl ring being connected with azoles nitrogen in cyclic metal complexes agent structure, this methyl group plays chemically modified effect, can realize the adjusting to this organic iridium metal complex emission wavelength, thereby obtain the phosphorescent emissions of different yellow-green colour emission wavelengths, the emission wavelength of organic iridium metal complex in concrete embodiment 1 as below and embodiment 4.The existence of this methyl group can also produce space steric effect, reduces the interatomic direct effect of iridium metals, reduces the self-quenching phenomenon of triplet exciton, thereby has ensured the electroluminescent intensity of this organic iridium metal complex.In order to make the organic iridium metal complex of above-described embodiment there is more suitable yellow green light wavelength, obtain more excellent electroluminescent properties, and better produce space steric effect, as preferred embodiment, this organic iridium metal complex is preferably organic iridium metal complex of above-mentioned molecular structural formula (I 2) to (I 11).
Correspondingly, the embodiment of the present invention also provides one to prepare the method for organic iridium metal complex of 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. utilize compd A to prepare chlorine bridge dipolymer B: in the environment of anaerobic, described compd A to be carried out to thermal backflow with hydration iridous chloride or the sub-iridium acid of hydration chlorine sodium in reaction solvent and react, generate the chlorine bridge dipolymer B of following structural formula general formula;
S03. utilize chlorine bridge dipolymer B to prepare organic iridium metal complex of general formula of molecular structure (I): in the environment of anaerobic, by the chlorine bridge dipolymer B and 2 preparing in step S02,2,6,6-tetramethyl--3,5-heptadione carries out thermal backflow reaction in reaction solvent, and purifying obtains organic iridium metal complex of described general formula of molecular structure (I).
Particularly, in above-mentioned steps S01, the R in compd A molecular structural formula 1, R 2, R 3, R 4identical or not identical is H or methyl.Due to the cyclic metal complexes structure of the organic iridium metal complex of compd A above-described embodiment.Therefore, compd A at least has and is similar to if (I 1) of organic iridium metal complex of above-mentioned general formula of molecular structure (I) is to 15 kinds of structural formulas of (I 15), in order to save length, does not repeat them here.
As preferred embodiment, above-claimed cpd A can be prepared as follows:
S011: by the compound N of following structural formula general formula 0generate compound N through cyclization 1;
S012: by compound N 1with alkaline metal iodide generation substitution reaction, generate compound N 2;
S013: in the environment of anaerobic, by compound N 2under alkaline condition, there is substitution reaction with carbazole, generate described compd A;
Wherein, the compound N in step S011 to S013 0, compound N 1and compound N 2r in molecular structural formula 1, R 2, R 3, R 4identical or not identical is H or methyl;
In above-mentioned steps S011, compound N 0cyclization can specifically carry out as follows:
By above-claimed cpd N 0be placed in and contain cupric sulfate pentahydrate, NH 4in the aqueous ethanolic solution of OH, carry out thermal backflow generation cyclization, generate compound N 1, wherein, cupric sulfate pentahydrate and compound N 0mol ratio be preferably (5～7): 1, NH 4oH and compound N 0mol ratio be preferably (16～18.75): 1.In one embodiment, this cupric sulfate pentahydrate, NH 4oH and compound N 0mole dosage than preferably but be not only 24:74:4.Particularly, the chemical formula of this cyclization is as follows:
After the thermal backflow cyclization of step S011, reacted product is filtered, after purifying and drying treatment, obtains brown needle-like crystals and be pure compound N 1.The method of this purifying can directly adopt washed several times with water.Due to compound N 0be the reactant of preparing above-claimed cpd A, and contain R in its phenyl group 1, R 2, R 3, R 4identical or not identical is H or methyl, therefore, and compound N 1at least have and be similar to as 15 of above-mentioned compd A kinds of structural formulas, in order to save length, do not repeat them here.
In above-mentioned steps S012, N 1can specifically carry out as follows with alkaline metal iodide generation substitution reaction:
The compound N that step S011 is generated 1be dissolved in the mixing solutions of acetic acid and hydrochloric acid composition, being heated to 75～85 DEG C obtains being cooled to 0～5 DEG C after brown suspension, drip again the aqueous solution of Sodium Nitrite, after stirring, add potassium iodide aqueous solution, question response mixed solution rises to after room temperature naturally, is heated to 45～55 DEG C and reacts, and then carries out solid-liquid separation, washing, purifying, obtain compound N 2.Wherein, Sodium Nitrite and compound N 1mol ratio be preferably 1.2～1.5:1; Potassiumiodide and compound N 1mol ratio be preferably 1.2～1.6.Particularly, the chemical equation of this substitution reaction is as follows:
Washing in this step S012 can be used saturated sodium bicarbonate, water and normal hexane washing successively, and purifying can adopt chromatographic purification, is the n-hexane/acetone mixed solution of 20:1 for eluent can adopt volume ratio.Due to compound N 1at least have and be similar to as 15 of above-mentioned compd A kinds of structural formulas, therefore, compound N 2at least have and be similar to as 15 of above-mentioned compd A kinds of structural formulas, in order to save length, do not repeat them here.
In above-mentioned steps S013, the environment of anaerobic can be vacuum or be full of rare gas element and realize, and be preferably full of rare gas element and 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 has ensured the stable of reactant, improves the yield of compd A.Alkaline condition in this step S013 can be the dimethylsulfoxide solvent that is dissolved with cuprous bromide, cesium carbonate.Therefore, this compound N 2and the substitution reaction between carbazole preferably by compound N 2, carbazole, cuprous bromide, cesium carbonate be dissolved in dimethylsulfoxide solvent and under thermal backflow condition and react, its chemical equation is as follows:
Therefore, in above-mentioned steps S013, compound N 2with the mole dosage of the mole theory of carbazole than being 1:1, in order to make compound N 2fully complete reaction, compound N 2be preferably > 1:1 with the mole dosage ratio of carbazole, as 1:1.09～1.3.In addition, in a preferred embodiment, cuprous bromide, cesium carbonate are preferably (0.2～0.4) with the mole dosage ratio of triazole compounds: (1.5～2.2): 1; Wherein, compound N 2concentration in methyl-sulphoxide is 0.11～0.183mol/L.
After the thermal backflow cyclization of step S013, reacted product is filtered, after purifying and drying treatment, obtains orange/yellow solid and be pure compd A.The method of this purifying can be, after the solid steaming after filtering is desolventized, to adopt silica gel column chromatography separating-purifying, and eluent is acetone and normal hexane mixed solution, as the acetone/normal hexane mixed solution taking volume ratio as 1:24.
In above-mentioned steps S02, hydration iridous chloride can be expressed as IrCl 3xH 2o, the sub-iridium acid of hydration chlorine 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, hydration iridous chloride, the sub-iridium acid of hydration chlorine sodium can also be also other hydrates.
The temperature of the thermal backflow reaction in this step S02 is determined according to the boiling point characteristic of selected reaction solvent.And this reaction solvent is preferably the mixture of 2-methyl cellosolve, cellosolvo, 2 methyl chloride, 3 methyl chloride at least one or 2-methyl cellosolve, cellosolvo, 2 methyl chloride, 3 methyl chloride at least one and distilled water.The more preferably mixture of 2-methyl cellosolve and distilled water.Therefore, the temperature when temperature of thermal backflow reaction is preferably the thermal backflow of this preferred reaction solvent in this step S02, at this preferred thermal backflow temperature, the time of thermal backflow reaction is preferably 20～30 hours.Certainly, this reaction solvent also can be selected 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 and realize.Realize oxygen-free environment and more easily realize owing to being full of rare gas element, therefore, be preferably full of rare gas element and 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 has ensured the stable of reactant, improves the yield of chlorine bridge dipolymer B.
Compd A in this step S02 is as follows with the chemical equation that hydration iridous chloride or the sub-iridium acid of hydration chlorine sodium react through thermal backflow:
Therefore, in above-mentioned steps S02, compd A is 2:1 with the mole dosage ratio of hydration iridous chloride or the sub-iridium acid of hydration chlorine sodium theory, therefore, in order to allow the abundant complete reaction of the sub-iridium acid sodium of hydration iridous chloride or hydration chlorine, the be preferably >=2:1 of mole dosage ratio of the sub-iridium acid of compd A and iridous chloride or hydration chlorine sodium, be preferably (2～4): 1, more preferably (2.2～4): 1.Wherein, the concentration range of this iridic compound in reaction solvent is preferably 0.05～0.25M.Certainly, also can allow compd A fully react, therefore, the be preferably≤2:1 of mole dosage ratio of the sub-iridium acid of compd A and hydration iridous chloride or hydration chlorine sodium.
After the thermal backflow cyclization of step S02, reacted product is filtered, after purifying and drying treatment, obtains pure compd B.The method of this purifying can be carried out as follows:
Reacted mixed solution is extracted, and the organic phase anhydrous magnesium sulfate drying that extraction obtains, filters, and steaming desolventizes.Crude product is carried out to silica gel column chromatography separating-purifying, and eluent is acetone and normal hexane mixed solution, as the acetone/normal hexane mixed solution taking volume ratio as 1:4.
Because the compd B of preparation contains compd A cyclic metal complexes agent structure, again because compd A at least exists 15 kinds of structural formulas mentioned above, therefore compd B equally at least has and is similar to as 15 of this compd A kinds of structural formulas, in order to save length, does not repeat them here.
In above-mentioned steps S03, the temperature of thermal backflow reaction is also to determine according to the boiling point characteristic of selected reaction solvent.And this reaction solvent be preferably 2-methyl cellosolve, cellosolvo, 2 methyl chloride, 3 methyl chloride at least one.More preferably 2-methyl cellosolve.Therefore, the temperature when temperature of thermal backflow reaction is preferably the thermal backflow of this preferred reaction solvent in this step S03, at this preferred thermal backflow temperature, the time of thermal backflow reaction is preferably 1～5 hour.Certainly, this reaction solvent also can be selected 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.In addition, also can add alkaline matter at this reaction solvent, carry and make this this reaction solvent be alkalescence, to improve the speed of reaction in step S03, this alkaline matter is preferably the alkaline matter such as sodium carbonate, salt of wormwood.Preferably 8～12 times of compd B molar weight of the molar weight that this alkaline matter adds.
Oxygen-free environment in this step S03 can be vacuum or be full of rare gas element and realize.Realize oxygen-free environment and more easily realize owing to being full of rare gas element, therefore, be preferably full of rare gas element and 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 has ensured the stable of reactant, improves the yield of organic iridium metal complex of general formula of molecular structure (I).
In this step S03 2,2,6,6-tetramethyl--3, the chemical equation that 5-heptadione reacts through thermal backflow with compd B is as follows:
Therefore, in above-mentioned steps S03 2,2,6,6-tetramethyl--3,5-heptadione is 2:1 with the mole dosage ratio of compd B theory, in order to make the abundant complete reaction of compd B, 2,2,6,6-tetramethyl--3, be preferably >=the 2:1 of mole dosage ratio of 5-heptadione and compd B, is preferably (2～4): 1, and more preferably (2.4～3.2): 1.Wherein, the concentration of compd B in reaction solvent is preferably 0.01～0.02mol/L.
After the thermal backflow cyclization of step S03, reacted product is filtered, after purifying and drying treatment, obtains organic iridium metal complex of pure general formula of molecular structure (I).The method of this purifying can, with reference to the purification process about compd B in above-mentioned steps S02, specifically be carried out as follows:
Reacted mixed solution is extracted, and the organic phase anhydrous magnesium sulfate drying that extraction obtains, filters, and steaming desolventizes.Crude product is carried out to silica gel column chromatography separating-purifying, and eluent is acetone and normal hexane mixed solution, as the acetone/normal hexane mixed solution taking volume ratio as 1:99.
Above-mentioned organic iridium metal complex preparation method only need carry out reactant thermal backflow reaction, and without special equipment and environmental requirement, its preparation method technique is simple, and productive rate is high, and mild condition, is easy to operate and control, and is suitable for suitability for industrialized production.
Have as the performance of the jaundice green glow of above-mentioned excellence just because of the organic iridium metal complex of above-described embodiment, and can be by the group in cyclic metal complexes agent structure as the adjusting of methyl group to emission wavelength, charge transport properties is good simultaneously, electroluminescent properties excellence, therefore, this organic iridium metal complex can be used as the application of yellow green light phosphor material in organic electroluminescence device, EL cold light film or electrochemical cell luminescent device.In application process, can be by organic embodiment of the present invention iridium metal complex and other luminescent material compound uses, prepare the electroluminescent device of the excellent white light that sets out, as by compound to the organic iridium metal complex of the embodiment of the present invention and the purple light phosphor material of jaundice green glow, prepare the white light parts with high electroluminescent intensity.The existing electroluminescent device that emits white light generally adopts the compound of ruddiness, green glow and blue light material to realize, the organic iridium metal complex of the embodiment of the present invention can be by emitting white light with purple light phosphor material is compound, therefore, the organic iridium metal complex of the embodiment of the present invention has been realized another kind of approach and has been prepared the electroluminescent device emitting white light.
Particularly, when the organic iridium metal complex of above-described embodiment as yellow green light phosphor material at organic electroluminescence device (organic electroluminescent LED, OLED), when application in, 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 according to the stacked setting of routine.In the luminescent layer of this organic electroluminescence device, contain the organic iridium metal complex of above-described embodiment, the material selection material known in this field of other each layer of structure, its preparation method also can be according to the existing method preparation in this area.
Particularly, when the organic iridium metal complex of above-described embodiment is as yellow green light phosphor material when the application 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, in the luminescent layer of this electrochemical cell luminescent device, contain the organic iridium metal complex of above-described embodiment, the material selection material known in this field of anode, negative electrode, its preparation method also can be according to the existing method preparation in this area.
Now in conjunction with the embodiments, the present invention is further elaborated.
Embodiment 1
Two [5-(9 '-carbazyl)-2-phenyl-1,2,3-benzotriazole-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex and synthetic method thereof:
(1) 5-amino-2-phenyl-1,2,3-benzotriazole synthetic:
By 9.95g (0.04mol) 2, the two aminophenyl nitrogen benzide hydrochlorides of 4-, 59.93g (0.24mol) cupric sulfate pentahydrate, 100mL are containing 25.94g (0.74mol) NH 4back flow reaction 4h in the aqueous ethanolic solution that the OH aqueous solution is 1:1 in 350mL volume ratio; After reacting completely, ice bath is cooling, filters, and washed several times with water, is dried to obtain brown needle-like crystals 6.47g, and yield is 76.9%; Its chemical equation is as follows:
By 5-amino-2-phenyl-1, the result of 2,3-benzotriazole Structural Identification:
Mass spectrum (MS m/z): 210.1 (M +); Ultimate analysis: C12H10N4; Theoretical value: C, 68.56; H, 4.79; N, 26.65; Measured value: C, 68.63; H, 4.70; N, 26.67.The material that the above-mentioned reaction of this data acknowledgement obtains is 5-amino-2-phenyl-1,2,3-benzotriazole.
(2) the iodo-2-of 5-phenyl-1,2,3-benzotriazole synthetic:
8.4g (40mmol) 5-amino-2-phenyl-1,2,3-benzotriazole is dissolved in the mixing solutions of 150mL acetic acid and 60mL hydrochloric acid composition, is heated to 80 DEG C and obtains being cooled to 0 DEG C after brown suspension.The solution that 3.7g (54mmol) Sodium Nitrite is dissolved in to 20mL water composition slowly adds in reaction system, maintains all the time temperature of reaction system at 0～5 DEG C in adition process.Control temperature of reaction at 5 DEG C, after stirring reaction 45min, add by 9.6g (58mmol) potassiumiodide and be dissolved in the solution that 40mL water forms, question response mixed solution rises to after room temperature naturally, slowly be heated to 50 DEG C and stir 20min, naturally be chilled to room temperature, add Sodium Pyrosulfite to red disappearance in solution, solid collected by filtration, use successively saturated sodium bicarbonate, water and normal hexane washing, crude product silica gel column chromatography separating-purifying, n-hexane/acetone mixed solution taking volume ratio as 24.5:0.5 is eluent, steaming desolventizes, after dry, obtain sallow solid 7.71g, yield is 60.0%, its chemical equation is as follows:
By iodo-5-2-phenyl-1,2,3-benzotriazole Structural Identification:
Mass spectrum (MS m/z): 321.0 (M +); Ultimate analysis: C12H8IN3; Theoretical value: C, 44.88; H, 2.51; I, 39.52; N, 13.09; Measured value: C, 44.83; H, 2.58; I, 39.46; N, 13.13.The material that the above-mentioned reaction of this data acknowledgement obtains is the iodo-2-of 5-phenyl-1,2,3-benzotriazole.
(3) 5-(9 '-carbazyl)-2-phenyl-1,2,3-benzotriazole synthetic:
Under argon shield; 1.00g (6.00mmol) carbazole, the iodo-2-of 1.77g (5.50mmol) 5-phenyl-1,2; 3-benzotriazole, 1.02g (1.10mmol) three (triphenylphosphine) cuprous bromide (Cu (PPh 3) 3br) and 2.69g (8.25mmol) cesium carbonate be dissolved in 30mL methyl-sulphoxide, under reflux state, react 8h.Reaction finishes rear methylene dichloride and water treatment mixed solution.Anhydrous sodium sulfate drying organic layer, filters, and steaming desolventizes.Gained residue silica gel column chromatography separating-purifying, the n-hexane/acetone mixed solution taking volume ratio as 24:1 is eluent, and steaming desolventizes, and after being dried, obtains yellow solid 1.25g, and yield is 63.0%; Its chemical equation is as follows:
By 5-(9 '-carbazyl)-2-phenyl-1, the result of 2,3-benzotriazole Structural Identification:
Mass spectrum (MS m/z): 360.1 (M+); Ultimate analysis: C24H16N4; Theoretical value: C, 79.98; H, 4.47; N, 15.55; Measured value: C, 79.94; H, 4.55; N, 15.51.The material that the above-mentioned reaction of this data acknowledgement obtains is 5-(9 '-carbazole)-2-phenyl-1,2,3-benzotriazole.
(4) main part is 5-(9 '-carbazyl)-2-phenyl-1,2,3-benzotriazole dimeric synthetic containing iridium dichloro:
Under argon shield, 0.35g (1mmol) three hydration iridous chlorides, 1.08g (3mmol) 5-(9 '-carbazole)-2-phenyl-1,2,3-benzotriazole is dissolved in the mixed solvent of cellosolvo that 30mL volume ratio is 3:1 and distilled water composition, and heating makes its back flow reaction 24h; Be chilled to after room temperature, filter and collect the crystal forming in reaction mixture, with distilled water and normal hexane washing, vacuum-drying, obtains crude product solid 0.42g successively, and yield is 44.4%; Its chemical equation is as follows:
(5) two [5-(9 '-carbazyl)-2-phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) closes the synthetic of iridium metal complex:
Under argon shield, the main part of 0.95g (0.5mmol) is 5-(9 '-carbazyl)-2-phenyl-1,2,3-benzotriazole containing iridium dichloro dimer, 0.28g (1.5mmol) 2,2,6,6-tetramethyl--3,5-heptadione and 0.53g (5mmol) sodium carbonate is dissolved in the 20mL2-ethoxy ethanol solvent of degasification, and heating makes its back flow reaction 5h; After reacting completely, be with reaction mixture to be naturally chilled to room temperature, by chloroform and distilled water extracted several times, organic phase anhydrous magnesium sulfate drying, filter, rotation is steamed and is desolventized, crude product silica gel column chromatography separating-purifying, acetone/normal hexane mixed solution taking volume ratio as 1:30 is eluent, steaming desolventizes, the dry rear final pure substance 0.48g that obtains, and yield is 43.9%; Its chemical equation is as follows:
This pair [5-(9 '-carbazyl)-2-phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) closed iridium metal complex and carries out the result of Structural Identification:
Mass spectrum (MS m/z): 1094.4 (M+); Ultimate analysis: C59H49IrN8O2; Theoretical value: C, 64.76; H, 4.51; Ir, 17.57; N, 10.24; O, 2.92; Measured value: C, 64.72; H, 4.58; Ir, 17.51; N, 10.30; O, 2.89.The material that the above-mentioned reaction of above data acknowledgement obtains is that two [5-(9 '-carbazyl)-2-phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3, the 5-heptadione) of title complex close iridium metal complex.
Two [5-(9 '-carbazyl)-2-phenyl-1 prepared by the present embodiment 1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex and carry out spectroscopic analysis, analytical results as shown in Figure 2, transverse axis is emission wavelength (nm of unit), and the longitudinal axis is the photoluminescence intensity (a.u.) after normalization method, and iridium metal complex is CH at 298K temperature 2cl 2solution (～10 -5the maximum emission peak of middle emmission spectrum M), at 564nm place, therefore, can be used as yellow green light electroluminescent material and is widely used in technical field of organic electroluminescence.
In addition organic iridium metal complex concentration of, being prepared by the present embodiment 1 is 10 -5the CH of M 2cl 2solution is at 298K temperature, with the fac-Ir under the same terms (ppy) 3cH 2cl 2solution is standard (Φ ph=0.40), record the Φ of end product pL=0.40, iridium metal complex prepared by visible the present embodiment 1 has higher internal quantum efficiency and electroluminescent efficiency as electroluminescent organic material.
Embodiment 2
Two [5-(9 '-carbazyl)-2-(6 '-methyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex and synthetic method thereof:
(1) 5-amino-2-(2 '-methyl) phenyl-1,2,3-benzotriazole synthetic:
By 10.51g (0.04mol) 2, two aminophenyl-the 2 '-methyl-benzene hydrochlorides of 4-, 59.93g (0.24mol) cupric sulfate pentahydrate, 100mL are containing 25.94g (0.74mol) NH 4back flow reaction 4h in the aqueous ethanolic solution that the OH aqueous solution is 1:1 in 350mL volume ratio; After reacting completely, ice bath is cooling, filters, and washed several times with water, is dried to obtain brown needle-like crystals 5.74g, and yield is 64.0%;
(2) the iodo-2-of 5-(2 ’ ?methyl) phenyl-1,2,3-benzotriazole synthetic:
8.97g (40mmol) 5-amino-2-(2 '-methyl) phenyl-1,2,3-benzotriazole is dissolved in the mixing solutions of 150mL acetic acid and 60mL hydrochloric acid composition, is heated to 80 DEG C and obtains being cooled to 0 DEG C after brown suspension.The solution that 3.86g (56mmol) Sodium Nitrite is dissolved in to 20mL water composition slowly adds in reaction system, maintains all the time temperature of reaction system at 0～5 DEG C in adition process.Control temperature of reaction at 5 DEG C, after stirring reaction 45min, add by 9.96g (60mmol) potassiumiodide and be dissolved in the solution that 40mL water forms.Question response mixed solution rises to after room temperature naturally, is slowly heated to 50 DEG C and stirs 20min.Naturally be chilled to room temperature, add Sodium Pyrosulfite to red disappearance in solution.Solid collected by filtration, successively with saturated sodium bicarbonate, water and normal hexane washing.Crude product silica gel column chromatography separating-purifying, the n-hexane/acetone mixed solution taking volume ratio as 40:1 is eluent, and steaming desolventizes, and after being dried, obtains sallow solid 5.76g, and yield is 43.0%.
(3) 5-(9 '-carbazyl)-2-(2 '-methyl) phenyl-1,2,3-benzotriazole synthetic:
1.01g (6.05mmol) carbazole, the iodo-2-of 1.84g (5.50mmol) 5-(2 '-methyl) phenyl-1,2,3-benzotriazole, 2.05g (2.2mmol) three (triphenylphosphine) cuprous bromide (Cu (PPh 3) 3br) and 3.58g (11mmol) cesium carbonate be dissolved in 35mL methyl-sulphoxide, under reflux state, react 8h.Methylene dichloride and water treatment mixed solution after reaction finishes.Anhydrous sodium sulfate drying organic layer, filters, and steaming desolventizes.Gained residue silica gel column chromatography separating-purifying, the n-hexane/acetone mixed solution taking volume ratio as 20:1 is eluent, and steaming desolventizes, and after being dried, obtains yellow solid 1.05g, and yield is 51.0%.
(4) main part is 5-(9 '-carbazyl)-2-(2 '-methyl) phenyl-1,2,3-benzotriazole dimeric synthetic containing iridium dichloro:
Under argon shield, 0.35g (1mmol) three hydration iridous chlorides, 0.94g (2.5mmol) 5-(9 '-carbazyl)-2-(2 '-methyl) phenyl-1,2,3-benzotriazole is dissolved in the mixed solvent of cellosolvo that 25mL volume ratio is 3:1 and distilled water composition, and heating makes its back flow reaction 24h; Be chilled to after room temperature, filter and collect the crystal forming in reaction mixture, successively with distilled water and normal hexane washing.Vacuum-drying, obtains crude product solid 0.34g, and yield is 34.9%.
(5) two [5-(9 '-carbazyl)-2-(6 '-methyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium metal complex:
Under argon shield, the main part of 0.98g (0.5mmol) is 5-(9 '-carbazyl)-2-(2 '-methyl) phenyl-1, 2, 3-benzotriazole containing iridium dichloro dimer, 0.28g (1.5mmol) 2, 2, 6, 6-tetramethyl--3, 5-heptadione and 0.53g (5mmol) sodium carbonate is dissolved in the 20mL2-ethoxy ethanol solvent of degasification, heating makes its back flow reaction 5h, after reacting completely, be with reaction mixture to be naturally chilled to room temperature, by chloroform and distilled water extracted several times, organic phase anhydrous magnesium sulfate drying, filter, rotation is steamed and is desolventized, crude product silica gel column chromatography separating-purifying, acetone/normal hexane mixed solution taking volume ratio as 1:30 is eluent, steaming desolventizes, the final pure substance 0.31g that obtains after dry, yield is 27.6%, it is as follows that two [5-(9 '-carbazyl)-2-(6 '-methyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex chemical structural formula:
Structural Identification:
Mass spectrum (MS m/z): 1122.4 (M+); Ultimate analysis: C61H53IrN8O2; Theoretical value: C, 65.28; H, 4.76; Ir, 17.13; N, 9.98; O, 2.85; Measured value: C, 65.24; H, 4.83; Ir, 17.15N, 9.91; O, 2.87.The material that the above-mentioned reaction of above data acknowledgement obtains is two [5-(9 '-carbazyl)-2-(6 '-methyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex.
Two [5-(9 '-carbazyl)-2-(6 '-methyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) prepared by the present embodiment 2 close iridium metal complex at 298K temperature, CH 2cl 2solution (～10 -5the maximum emission peak of middle emmission spectrum M) is at 557nm place.In addition, concentration is 10 -5the CH of M iridium metal complex 2cl 2solution is at 298K temperature, with the fac-Ir under the same terms (ppy) 3cH 2cl 2solution is standard (Φ ph=0.40), record the Φ of end product pL=0.22.Therefore the iridium metal complex that, prepared by the present embodiment 2 has higher internal quantum efficiency and electroluminescent efficiency as electroluminescent organic material.
Embodiment 3:
Two [5-(9 '-carbazyl)-2-(5 '-methyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex and synthetic method thereof:
(1) 5-amino-2-(3 '-methyl) phenyl-1,2,3-benzotriazole synthetic:
By 10.51g (0.04mol) 2, two aminophenyl-the 3 '-methyl-benzene hydrochlorides of 4-, 59.93g (0.24mol) cupric sulfate pentahydrate, 100mL are containing 25.94g (0.74mol) NH 4back flow reaction 4h in the aqueous ethanolic solution that the OH aqueous solution is 1:1 in 350mL volume ratio; After reacting completely, ice bath is cooling, filters washed several times with water.Be dried to obtain brown needle-like crystals 5.92g, yield is 66.0%;
(2) the iodo-2-of 5-(3 '-methyl) phenyl-1,2,3-benzotriazole synthetic:
8.97g (40mmol) 5-amino-2-(3 '-methyl) phenyl-1,2,3-benzotriazole is dissolved in the mixing solutions of 150mL acetic acid and 60mL hydrochloric acid composition, is heated to 80 DEG C and obtains being cooled to 0 DEG C after brown suspension.The solution that 3.59g (52mmol) Sodium Nitrite is dissolved in to 20mL water composition slowly adds in reaction system, in adition process, maintain all the time temperature of reaction system at 0～5 DEG C, control temperature of reaction at 5 DEG C, after stirring reaction 45min, add by 10.62g (64mmol) potassiumiodide and be dissolved in the solution that 40mL water forms, question response mixed solution rises to after room temperature naturally, slowly be heated to 50 DEG C and stir 20min, naturally be chilled to room temperature, add Sodium Pyrosulfite to red disappearance in solution, solid collected by filtration, use successively saturated sodium bicarbonate, water and normal hexane washing, crude product silica gel column chromatography separating-purifying, n-hexane/acetone mixed solution taking volume ratio as 40:1 is eluent, steaming desolventizes, after dry, obtain sallow solid 5.90g, yield is 44.0%,
(3) 5-(9 '-carbazyl)-2-(3 '-methyl) phenyl-1,2,3-benzotriazole synthetic:
Under argon shield; 1.10g (6.60mmol) carbazole; the iodo-2-of 1.84g (5.50mmol) 5-(3 '-methyl) phenyl-1; 2; 3-benzotriazole, 1.53g (1.65mmol) three (triphenylphosphine) cuprous bromide (Cu (PPh 3) 3br) and 3.94g (12.1mmol) cesium carbonate be dissolved in 40mL methyl-sulphoxide, under reflux state, react 8h, methylene dichloride and water treatment mixed solution after reaction finishes, anhydrous sodium sulfate drying organic layer, filters, steaming desolventizes, gained residue silica gel column chromatography separating-purifying, the n-hexane/acetone mixed solution taking volume ratio as 20:1 is eluent, steaming desolventizes, after dry, obtain yellow solid 1.03g, yield is 49.5%;
(4) main part is 5-(9 '-carbazyl)-2-(3 '-methyl) phenyl-1,2,3-benzotriazole dimeric synthetic containing iridium dichloro:
Under argon shield, 0.35g (1mmol) three hydration iridous chlorides, 0.82g (2.2mmol) 5-(9 '-carbazyl)-2-(3 '-methyl) phenyl-1,2,3-benzotriazole is dissolved in the mixed solvent of cellosolvo that 20mL volume ratio is 3:1 and distilled water composition, and heating makes its back flow reaction 24h; Be chilled to after room temperature, filter and collect the crystal forming in reaction, successively with distilled water and normal hexane washing; Vacuum-drying, obtains crude product solid 0.29g, and yield is 29.7%.
(5) two [5-(9 '-carbazyl)-2-(5 '-methyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium metal complex:
Under argon shield, the main part of 0.98g (0.5mmol) is 5-(9 '-carbazyl)-2-(3 '-methyl) phenyl-1, 2, 3-benzotriazole containing iridium dichloro dimer, 0.28g (1.5mmol) 2, 2, 6, 6-tetramethyl--3, 5-heptadione and 0.53g (5mmol) sodium carbonate is dissolved in the 20mL2-ethoxy ethanol solvent of degasification, heating makes its back flow reaction 5h, after reacting completely, be with reaction mixture to be naturally chilled to room temperature, by chloroform and distilled water extracted several times, organic phase anhydrous magnesium sulfate drying, filter, rotation is steamed and is desolventized, crude product silica gel column chromatography separating-purifying, acetone/normal hexane mixed solution taking volume ratio as 1:30 is eluent, steaming desolventizes, the final pure substance 0.34g that obtains after dry, yield is 30.3%, it is as follows that two [5-(9 '-carbazyl)-2-(5 '-methyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex chemical structural formula:
Two [5-(9 '-carbazyl)-2-(5 '-methyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) are closed to iridium metal complex structure to be identified:
Mass spectrum (MS m/z): 1122.4 (M+); Ultimate analysis: C61H53IrN8O2; Theoretical value: C, 65.28; H, 4.76; Ir, 17.13; N, 9.98; O, 2.85; Measured value: C, 65.33; H, 4.70; Ir, 17.17N, 9.92; O, 2.88.The material that the above-mentioned reaction of this data acknowledgement obtains is that two [5-(9 '-carbazyl)-2-(5 '-methyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) closes iridium metal complex.
Two [5-(9 '-carbazyl)-2-(5 '-methyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) prepared by the present embodiment 3 closes iridium metal complex CH at 298K temperature 2cl 2solution (～10 -5the maximum emission peak of middle emmission spectrum M) is at 560nm place.In addition, concentration is 10 -5the CH of M iridium metal complex 2cl 2solution is at 298K temperature, with the fac-Ir under the same terms (ppy) 3cH 2cl 2solution is standard (Φ ph=0.40), record the Φ of end product pL=0.24.Therefore the iridium metal complex that, prepared by the present embodiment 3 has higher internal quantum efficiency and electroluminescent efficiency as electroluminescent organic material.
Embodiment 4
Two [5-(9 '-carbazyl)-2-(4 ', 6 '-dimethyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex and synthetic method thereof:
(1) 5-amino-2-(2 ', 4 '-dimethyl) phenyl-1,2,3-benzotriazole synthetic:
By 11.07g (0.04mol) 2, the two aminophenyls-2 ' of 4-, 4 '-dimethyl nitrogen benzide hydrochloride, 59.93g (0.24mol) cupric sulfate pentahydrate, 100mL are containing 25.94g (0.74mol) NH 4back flow reaction 4h in the aqueous ethanolic solution that the OH aqueous solution is 1:1 in 350mL volume ratio; After reacting completely, ice bath is cooling.Filter, washed several times with water, is dried to obtain brown needle-like crystals 4.76g, and yield is 49.9%;
(2) the iodo-2-of 5-(2 ', 4 ’ ?dimethyl) phenyl-1,2,3-benzotriazole synthetic:
9.53g (40mmol) 5-amino-2-(2 ', 4 '-dimethyl) phenyl-1, 2, 3-benzotriazole is dissolved in the mixing solutions of 150mL acetic acid and 60mL hydrochloric acid composition, being heated to 80 DEG C obtains being cooled to 0 DEG C after brown suspension, the solution that 4.14g (60mmol) Sodium Nitrite is dissolved in to 20mL water composition slowly adds in reaction system, in adition process, maintain all the time temperature of reaction system at 0～5 DEG C, control temperature of reaction at 5 DEG C, after stirring reaction 45min, add by 9.30g (56mmol) potassiumiodide and be dissolved in the solution that 40mL water forms, question response mixed solution rises to after room temperature naturally, slowly be heated to 50 DEG C and stir 20min, naturally be chilled to room temperature, add Sodium Pyrosulfite to red disappearance in solution, solid collected by filtration, use successively saturated sodium bicarbonate, water and normal hexane washing, crude product silica gel column chromatography separating-purifying, n-hexane/acetone mixed solution taking volume ratio as 20:1 is eluent, steaming desolventizes, after dry, obtain solid 4.19g, yield is 30.0%,
(3) 5-(9 '-carbazyl)-2-(2 ', 4 '-dimethyl) phenyl-1,2,3-benzotriazole synthetic:
Under argon shield; 1.20g (7.15mmol) carbazole; the iodo-2-(2 ' of 1.92g (5.50mmol) 5-; 4 '-dimethyl) phenyl-1; 2; 3-benzotriazole, 1.86g (2.00mmol) three (triphenylphosphine) cuprous bromide (Cu (PPh 3) 3br) and 3.22g (9.90mmol) cesium carbonate be dissolved in 45mL methyl-sulphoxide, under reflux state, react 8h; Methylene dichloride and water treatment mixed solution after reaction finishes, anhydrous sodium sulfate drying organic layer, filter, steaming desolventizes, gained residue silica gel column chromatography separating-purifying, the n-hexane/acetone mixed solution taking volume ratio as 30:1 is eluent, steaming desolventizes, after dry, obtain solid 0.78g, yield is 40.2%;
(4) main part is 5-(9 '-carbazyl)--2-(2 ', 4 '-dimethyl) phenyl-1, and 2,3-benzotriazole dimeric synthetic containing iridium dichloro:
Under argon shield, 0.35g (1mmol) three hydration iridous chlorides, 1.09g (2.8mmol) 5-(9 '-carbazyl)-2-(2 ', 4 '-dimethyl) phenyl-1,2,3-benzotriazole is dissolved in the mixed solvent of cellosolvo that 30mL volume ratio is 3:1 and distilled water composition, and heating makes its back flow reaction 24h; Be chilled to after room temperature, filter and collect the crystal forming in reaction mixture, successively with distilled water and normal hexane washing.Vacuum-drying, obtains crude product solid 0.29g, and yield is 28.9%;
(5) two [5-(9 '-carbazyl)-2-(4 ', 6 '-dimethyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium metal complex:
Under argon shield, the main part of 1.01g (0.5mmol) is 5-(9 '-carbazyl)-2-(2 ', 4 '-dimethyl) phenyl-1, 2, 3-benzotriazole containing iridium dichloro dimer, 0.28g (1.5mmol) 2, 2, 6, 6-tetramethyl--3, 5-heptadione and 0.53g (5mmol) sodium carbonate is dissolved in the 20mL2-ethoxy ethanol solvent of degasification, heating makes its back flow reaction 5h, after reacting completely, be with reaction mixture to be naturally chilled to room temperature, by chloroform and distilled water extracted several times, organic phase anhydrous magnesium sulfate drying, filter, rotation is steamed and is desolventized, crude product silica gel column chromatography separating-purifying, acetone/normal hexane mixed solution taking volume ratio as 1:100 is eluent, steaming desolventizes, the final pure substance 0.29g that obtains after dry, yield is 25.2%, it is as follows that two [5-(9 '-carbazyl)-2-(4 ', 6 '-dimethyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex chemical structural formula:
Two [5-(9 '-carbazyl)-2-(4 ', 6 '-dimethyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) are closed to iridium metal complex and carry out Structural Identification:
Mass spectrum (MS m/z): 1150.42 (M +); Ultimate analysis: C63H57IrN8O2; Theoretical value: C, 65.78; H, 4.99; Ir, 16.71; N, 9.74; O, 2.78; Measured value: C, 65.74; H, 4.96; Ir, 16.83; N, 9.72; O, 2.75.The material that the above-mentioned reaction of this data acknowledgement obtains is two [5-(9 '-carbazyl)-2-(4 ', 6 '-dimethyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex.
Two [5-(9 '-carbazyl)-2-(4 ' prepared by the present embodiment 4,6 '-dimethyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex and carry out spectroscopic analysis, iridium metal complex is CH at 298K temperature 2cl 2solution (～10 -5the maximum emission peak of middle emmission spectrum M), at 568nm place, therefore, can be used as yellow green light electroluminescent material and is widely used in technical field of organic electroluminescence.
In addition organic iridium metal complex concentration of, being prepared by the present embodiment 4 is 10 -5the CH of M 2cl 2solution is at 298K temperature, with the fac-Ir under the same terms (ppy) 3cH 2cl 2solution is standard (Φ ph=0.40), record the Φ of end product pL=0.17, iridium metal complex prepared by visible the present embodiment 4 has higher internal quantum efficiency and electroluminescent efficiency as electroluminescent organic material.
Embodiment 5
Two [5-(9 '-carbazyl)-2-(5 ', 6 '-dimethyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex and synthetic method thereof:
(1) 5-amino-2-(2 ', 3 '-dimethyl) phenyl-1,2,3-benzotriazole synthetic:
11.07g (0.04mol) 2, the two aminophenyls-2 ' of 4-, 3 '-dimethyl nitrogen benzide hydrochloride, 69.91g (0.28mol) cupric sulfate pentahydrate, 100mL are containing 26.28g (0.75mol) NH 4back flow reaction 5h in the aqueous ethanolic solution that the OH aqueous solution is 1:1 in 350mL volume ratio; After reacting completely, ice bath is cooling, filters, and washed several times with water, is dried to obtain brown needle-like crystals 4.96g, and yield is 52.0%;
(2) the iodo-2-of 5-(2 ', 3 '-dimethyl) phenyl-1,2,3-benzotriazole synthetic:
9.53g (40mmol) 5-amino-2-(2 ', 3 '-dimethyl) phenyl-1,2,3-benzotriazole is dissolved in the mixing solutions of 150mL acetic acid and 60mL hydrochloric acid composition, is heated to 80 DEG C and obtains being cooled to 0 DEG C after brown suspension.The solution that 3.45g (50mmol) Sodium Nitrite is dissolved in to 20mL water composition slowly adds in reaction system, maintains all the time temperature of reaction system at 0～5 DEG C in adition process.Control temperature of reaction at 5 DEG C, after stirring reaction 45min, add by 8.63g (52mmol) potassiumiodide and be dissolved in the solution that 40mL water forms.Question response mixed solution rises to after room temperature naturally, is slowly heated to 50 DEG C and stirs 20min.Naturally be chilled to room temperature, add Sodium Pyrosulfite to red disappearance in solution.Solid collected by filtration, successively with saturated sodium bicarbonate, water and normal hexane washing.Crude product silica gel column chromatography separating-purifying, the n-hexane/acetone mixed solution taking volume ratio as 20:1 is eluent, and steaming desolventizes, and after being dried, obtains solid 3.91g, and yield is 28.0%;
(3) 5-(9 '-carbazyl)-2-(2 ', 3 '-dimethyl) phenyl-1,2,3-benzotriazole synthetic:
Under argon shield; 1.09g (6.50mmol) carbazole; the iodo-2-(2 ' of 1.92g (5.50mmol) 5-; 3 '-dimethyl) phenyl-1; 2; 3-benzotriazole, 1.67g (1.80mmol) three (triphenylphosphine) cuprous bromide (Cu (PPh 3) 3br) and 3.26g (10mmol) cesium carbonate be dissolved in 40mL methyl-sulphoxide, under reflux state, react 8h, methylene dichloride and water treatment mixed solution after reaction finishes, anhydrous sodium sulfate drying organic layer, filters, steaming desolventizes, gained residue silica gel column chromatography separating-purifying, the n-hexane/acetone mixed solution taking volume ratio as 30:1 is eluent, steaming desolventizes, after dry, obtain solid 0.75g, yield is 35.1%;
(4) main part is 5-(9 '-carbazyl)-2-(2 ', 3 '-dimethyl) phenyl-1,2,3-benzotriazole dimeric synthetic containing iridium dichloro:
Under argon shield, 0.35g (1mmol) three hydration iridous chlorides, 1.55g (4mmol) 5-(9 '-carbazyl)-2-(2 ', 3 '-dimethyl) phenyl-1,2,3-benzotriazole is dissolved in the mixed solvent of cellosolvo that 40mL volume ratio is 3:1 and distilled water composition, heating makes its back flow reaction 24h, be chilled to after room temperature, filter and collect the crystal forming in reaction mixture, successively with distilled water and normal hexane washing, vacuum-drying, obtains crude product solid 0.30g, and yield is 29.9%;
(5) two [5-(9 '-carbazyl)-2-(5 ', 6 '-dimethyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium metal complex:
Under argon shield, the main part of 1.01g (0.5mmol) is 5-(9 '-carbazyl)-2-(2 ', 3 '-dimethyl) phenyl-1, 2, 3-benzotriazole containing iridium dichloro dimer, 0.28g (1.5mmol) 2, 2, 6, 6-tetramethyl--3, 5-heptadione and 0.69g (5mmol) salt of wormwood is dissolved in the 20mL2-ethoxy ethanol solvent of degasification, heating makes its back flow reaction 5h, after reacting completely, be with reaction mixture to be naturally chilled to room temperature, by chloroform and distilled water extracted several times, organic phase anhydrous magnesium sulfate drying, filter, rotation is steamed and is desolventized, crude product silica gel column chromatography separating-purifying, acetone/normal hexane mixed solution taking volume ratio as 1:100 is eluent, steaming desolventizes, the final pure substance 0.28g that obtains after dry, yield is 24.3%, it is as follows that two [5-(9 '-carbazyl)-2-(5 ', 6 '-dimethyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex chemical structural formula:
The result of this iridium metal complex Structural Identification:
Mass spectrum (MS m/z): 1150.42 (M +); Ultimate analysis: C63H57IrN8O2; Theoretical value: C, 65.78; H, 4.99; Ir, 16.71; N, 9.74; O, 2.78; Measured value: C, 65.76; H, 5.05; Ir, 16.66; N, 9.77; O, 2.76.The material that the above-mentioned reaction of this data acknowledgement obtains is two [5-(9 '-carbazyl)-2-(5 ', 6 '-dimethyl) phenyl-1,2 of title complex, 3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex.
Two [5-(9 '-carbazyl)-2-(5 ', 6 '-dimethyl) phenyl-1,2 prepared by the present embodiment 5,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex CH at 298K temperature 2cl 2solution (～10 -5the maximum emission peak of middle emmission spectrum M) is at 553nm place.In addition the CH of this iridium metal complex of 10-5M, 2cl 2solution is at 298K temperature, with the fac-Ir under the same terms (ppy) 3cH 2cl 2solution is standard (Φ ph=0.40), record the Φ of end product pL=0.20.Therefore the iridium metal complex that, prepared by the present embodiment 5 has higher internal quantum efficiency and electroluminescent efficiency as electroluminescent organic material.
Embodiment 6:
Two [5-(9 '-carbazyl)-2-(3 ', 6 '-dimethyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex and synthetic method thereof:
(1) 5-amino-2-(2 ', 5 '-dimethyl) phenyl-1,2,3-benzotriazole synthetic:
11.07g (0.04mol) 2, the two aminophenyls-2 ' of 4-, 5 '-dimethyl nitrogen benzide hydrochloride, 62.42g (0.25mol) cupric sulfate pentahydrate, 100mL is containing 26.28g (0.75mol) NH 4back flow reaction 5h in the aqueous ethanolic solution that the OH aqueous solution is 1:1 in 350mL volume ratio.After reacting completely, ice bath is cooling.Filter washed several times with water.Be dried to obtain brown needle-like crystals 3.62g, yield is 38.0%;
(2) the iodo-2-of 5-(2 ', 5 '-dimethyl) phenyl-1,2,3-benzotriazole synthetic:
9.53g (40mmol) 5-amino-2-(2 ', 5 '-dimethyl) phenyl-1,2,3-benzotriazole is dissolved in the mixing solutions of 150mL acetic acid and 60mL hydrochloric acid composition, is heated to 80 DEG C and obtains being cooled to 0 DEG C after brown suspension.The solution that 3.31g (48mmol) Sodium Nitrite is dissolved in to 20mL water composition slowly adds in reaction system, maintains all the time temperature of reaction system at 0～5 DEG C in adition process.Control temperature of reaction at 5 DEG C, after stirring reaction 45min, add by 7.97g (48mmol) potassiumiodide and be dissolved in the solution that 40mL water forms; Question response mixed solution rises to after room temperature naturally, slowly be heated to 50 DEG C and stir 20min, naturally be chilled to room temperature, add Sodium Pyrosulfite to red disappearance in solution, solid collected by filtration, successively with saturated sodium bicarbonate, water and normal hexane washing, crude product silica gel column chromatography separating-purifying, the n-hexane/acetone mixed solution taking volume ratio as 20:1 is eluent, steaming desolventizes, after dry, obtain solid 4.19g, yield is 30.0%;
(3) 5-(9 '-carbazyl)-2-(2 ', 5 '-dimethyl) phenyl-1,2,3-benzotriazole synthetic:
Under argon shield; 1.07g (6.40mmol) carbazole; the iodo-2-(2 ' of 1.92g (5.50mmol) 5-; 5 '-dimethyl) phenyl-1; 2; 3-benzotriazole, 1.77g (1.90mmol) three (triphenylphosphine) cuprous bromide (Cu (PPh 3) 3br) and 3.26g (10mmol) cesium carbonate be dissolved in 50mL methyl-sulphoxide, under reflux state, react 8h.After reacting completely, be naturally chilled to room temperature, methylene dichloride and water treatment mixed solution.Anhydrous sodium sulfate drying organic layer, filters, and steaming desolventizes.; Gained residue silica gel column chromatography separating-purifying, the acetone/normal hexane mixed solution taking volume ratio as 1:30 is eluent, and steaming desolventizes, and after being dried, obtains solid 0.73g, and yield is 34.2%;
(4) main part is 5-(9 '-carbazyl)-2-(2 ', 5 '-dimethyl) phenyl-1,2,3-benzotriazole dimeric synthetic containing iridium dichloro:
Under argon shield, 0.35g (1mmol) three hydration iridous chlorides, 1.16g (3mmol) 5-diphenyl amino-2-(9 '-carbazyl) phenyl-1,2,3-benzotriazole is dissolved in the mixed solvent of cellosolvo that 25mL volume ratio is 3:1 and distilled water composition, and heating makes its back flow reaction 24h; Be chilled to after room temperature, filter and collect the crystal forming in reaction mixture, successively with distilled water and normal hexane washing.Vacuum-drying, obtains crude product and obtains crude product solid 0.19g, and yield is 18.9%;
(5) two [5-(9 '-carbazyl)-2-(3 ', 6 '-dimethyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium metal complex:
Under argon shield; the main part of 1.01g (0.5mmol) is 5-(9 '-carbazyl)-2-(2 '; 5 '-dimethyl) phenyl-1; 2,3-benzotriazole containing iridium dichloro dimer, 0.37g (2.0mmol) 2,2; 6; 6-tetramethyl--3,5-heptadione and 0.83g (5mmol) salt of wormwood is dissolved in the 20mL2-ethoxy ethanol solvent of degasification, and heating makes its back flow reaction 6h.After reacting completely, be with reaction mixture to be naturally chilled to room temperature, by chloroform and distilled water extracted several times.Organic phase anhydrous magnesium sulfate drying, filters, and rotation is steamed and desolventized.Crude product silica gel column chromatography separating-purifying, the acetone/normal hexane mixed solution taking volume ratio as 1:100 is eluent, steaming desolventizes, the dry rear final pure substance 0.24g that obtains, yield is 20.9%; It is as follows that two [5-(9 '-carbazyl)-2-(3 ', 6 '-dimethyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex chemical structural formula:
Structural Identification:
Mass spectrum (MS m/z): 1150.42 (M +); Ultimate analysis: C63H57IrN8O2; Theoretical value: C, 65.78; H, 4.99; Ir, 16.71; N, 9.74; O, 2.78; Measured value: C, 65.85; H, 4.90; Ir, 16.77; N, 9.66; O, 2.82.The material that the above-mentioned reaction of this data acknowledgement obtains is two [5-(9 '-carbazyl)-2-(3 ', 6 '-dimethyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione).
Two [5-(9 '-carbazyl)-2-(3 ', 6 '-dimethyl) phenyl-1,2 prepared by the present embodiment 6,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex CH at 298K temperature 2cl 2solution (～10 -5the maximum emission peak of middle emmission spectrum M) is at 568nm place.In addition, 10 -5the CH of this iridium metal complex of M 2cl 2solution is at 298K temperature, with the fac-Ir under the same terms (ppy) 3cH 2cl 2solution is standard (Φ ph=0.40), record the Φ of end product pL=0.12.Therefore the iridium metal complex that, prepared by the present embodiment 6 has higher internal quantum efficiency and electroluminescent efficiency as electroluminescent organic material.
Embodiment 7:
Two [5-(9 '-carbazyl)-2-(3 ', 5 '-dimethyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex and synthetic method thereof:
(1) 5-amino-2-(3 ', 5 '-dimethyl) phenyl-1,2,3-benzotriazole synthetic
11.07g (0.04mol) 2, the two amino-3 ' of 4-, 5 '-dimethyl nitrogen benzide hydrochloride, 74.90g (0.30mol) cupric sulfate pentahydrate, 100mL is containing 26.28g (0.75mol) NH 4back flow reaction 6h in the aqueous ethanolic solution that the OH aqueous solution is 1:1 in 350mL volume ratio; After reacting completely, ice bath is cooling, filters, and washed several times with water, is dried to obtain brown needle-like crystals 4.29g, and yield is 45.0%; Its
(2) the iodo-2-of 5-(3 ', 5 '-dimethyl) phenyl-1,2,3-benzotriazole synthetic:
9.53g (40mmol) 5-amino-2-(3 ', 5 '-dimethyl) phenyl-1,2,3-benzotriazole is dissolved in the mixing solutions of 150mL acetic acid and 60mL hydrochloric acid composition, is heated to 80 DEG C and obtains being cooled to 0 DEG C after brown suspension.The solution that 4.14g (60mmol) Sodium Nitrite is dissolved in to 20mL water composition slowly adds in reaction system, in adition process, maintain all the time temperature of reaction system at 0～5 DEG C, control temperature of reaction at 5 DEG C, after stirring reaction 45min, add by 9.96g (60mmol) potassiumiodide and be dissolved in the solution that 40mL water forms, question response mixed solution rises to after room temperature naturally, is slowly heated to 50 DEG C and stirs 20min; Naturally be chilled to room temperature, add Sodium Pyrosulfite to red disappearance in solution, solid collected by filtration, successively with saturated sodium bicarbonate, water and normal hexane washing; Crude product silica gel column chromatography separating-purifying, the n-hexane/acetone mixed solution taking volume ratio as 20:1 is eluent, and steaming desolventizes, and after being dried, obtains solid 4.61g, and yield is 33.0%;
(3) 5-(9 '-carbazyl)-2-(3 ', 5 '-dimethyl) phenyl-1,2,3-benzotriazole synthetic:
Under argon shield; 1.00g (6.00mmol) carbazole; the iodo-2-(3 ' of 1.92g (5.50mmol) 5-; 5 '-dimethyl) phenyl-1; 2,3-benzotriazole, 1.02g (1.10mmol) three (triphenylphosphine) cuprous bromide (Cu (PPh 3) 3br) and 2.69g (8.25mmol) cesium carbonate be dissolved in 30mL methyl-sulphoxide, heating makes its back flow reaction 8h; After reacting completely, naturally be chilled to room temperature, process mixed solution with methylene dichloride and distilled water, anhydrous sodium sulfate drying organic layer, filters, steaming desolventizes, gained residue silica gel column chromatography separating-purifying, the acetone/normal hexane mixed solution taking volume ratio as 1:30 is eluent, steaming desolventizes, after dry, obtain solid 0.85g, yield is 39.8%;
(4) main part is 5-(9 '-carbazyl)-2-(3 ', 5 '-dimethyl) phenyl-1,2,3-benzotriazole dimeric synthetic containing iridium dichloro:
Under argon shield, 0.35g (1mmol) three hydration iridous chlorides, 1.01g (2.6mmol) 5-(9 '-carbazyl)-2-(3 ', 5 '-dimethyl) phenyl-1,2,3-benzotriazole is dissolved in the mixed solvent of cellosolvo that 35mL volume ratio is 3:1 and distilled water composition, and heating makes its back flow reaction 24h; Be chilled to after room temperature, filter and collect the crystal forming in reaction mixture, successively with distilled water and normal hexane washing.Vacuum-drying, obtains crude product 0.32g, and yield is 31.9%; Crude product, without further purification, can directly drop into next step reaction;
(4) two [5-(9 '-carbazyl)-2-(3 ', 5 '-dimethyl) phenyl-1,2,3-benzotriazole-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the synthetic of iridium metal complex:
Under argon shield; the main part of 1.01g (0.5mmol) is 5-(9 '-carbazyl)-2-(3 '; 5 '-dimethyl) phenyl-1; 2,3-benzotriazole containing iridium dichloro dimer, 0.37g (2.0mmol) 2,2; 6; 6-tetramethyl--3,5-heptadione and 0.64g (5mmol) sodium carbonate is dissolved in the 25mL2-ethoxy ethanol solvent of degasification, and heating makes its back flow reaction 6h.After reacting completely, be with reaction mixture to be naturally chilled to room temperature, with chloroform and distilled water extracted several times, organic phase anhydrous magnesium sulfate drying, filter, rotation is steamed and is desolventized.Crude product silica gel column chromatography separating-purifying, the acetone/normal hexane mixed solution taking volume ratio as 1:100 is eluent, steaming desolventizes, the dry rear final pure substance 0.26g that obtains, yield is 22.6%; Its chemical equation is as follows:
Structural Identification:
Mass spectrum (MS m/z): 1150.42 (M +); Ultimate analysis: C63H57IrN8O2; Theoretical value: C, 65.78; H, 4.99; Ir, 16.71; N, 9.74; O, 2.78; Measured value: C, 65.70; H, 5.10; Ir, 16.66; N, 9.77; O, 2.77.The material that the above-mentioned reaction of this data acknowledgement obtains is two [5-(9 '-carbazyl)-2-(3 ', 5 '-dimethyl) phenyl-1,2 of title complex, 3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex.
Two [5-(9 '-carbazyl)-2-(3 ', 5 '-dimethyl) phenyl-1,2 prepared by the present embodiment 7,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex CH at 298K temperature 2cl 2solution (～10 -5the maximum emission peak of middle emmission spectrum M) is at 568nm place.In addition, 10 -5the CH of this iridium metal complex of M 2cl 2solution is at 298K temperature, with the fac-Ir under the same terms (ppy) 3cH 2cl 2solution is standard (Φ ph=0.40), record the Φ of end product pL=0.12.Therefore the iridium metal complex that, prepared by the present embodiment 7 has higher internal quantum efficiency and electroluminescent efficiency as electroluminescent organic material.
Application Example 1
Organic iridium metal complex organic electroluminescence device (OLED) of preparing containing 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, luminescent layer 33, electron transfer layer 34, electron injecting layer 35 and the cathode layer 4 that stack gradually combination to the structure of this OLED.Wherein, hole injection layer 31, hole transmission layer 32, luminescent layer 33, hole blocking layer 34, electron transfer layer 35, electron injecting layer 36 form organic function layer 3, in this luminescent layer 33, contain two [5-(9 '-carbazyl)-2-phenyl-1 prepared by embodiment 1,2,3-benzotriazole-N, C 2'] (2,2,6,6-tetramethyl--3,5-heptadione) close iridium metal complex.Its concrete structure the following is glass/ITO (100nm)/2-TNATA (60nm)/NPB (20nm)/CBP:8wt%Ir title complex (30nm)/BCP (10nm)/Alq 3(20nm)/Liq (2nm)/Al (100nm).
This OLED preparation method is as follows: in a glass substrate 1, depositing a layer thickness is 100nm, square resistance is that the tin indium oxide (ITO) of 10～20 Ω/mouths is as transparent anode 2, on anode 2, prepare successively by vacuum evaporation the 2-TNATA(4 that a layer thickness is 40nm, 4', 4''-tri-(N-(naphthalene-2-yl)-N-phenyl 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 '-phenylbenzene benzidine) hole mobile material is as hole transmission layer 32, a layer thickness is two [5-(9 '-carbazyl)-2-phenyl-1 of preparing doped with 8wt% embodiment 1 of 30nm, 2, 3-benzotriazole-N, C 2'] (2, 2, 6, 6-tetramethyl--3, 5-heptadione) close the CBP (N of iridium metal complex, two carbazyl-4 of N'-, 4'-dipyridyl) as luminescent layer 33, the BCP(2 that vacuum evaporation a layer thickness is successively 10nm on this luminescent layer 33 again, 9-dimethyl-4, 7-phenylbenzene-phenanthrolene) material is as hole blocking layer 34, thickness is that the Alq3 (three (oxine) aluminium) of 20nm is as electron transfer layer 35, thickness is that the Liq of 2nm is as electronic injection buffer layer 36, finally on buffer layer, adopt the metal A l that vacuum plating techniques of deposition thickness is 100nm, 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 567nm, and maximum current efficiency is 6.64cd/A, and maximum external quantum efficiency is 1.54%.
Application Example 2
Organic iridium metal complex organic electroluminescence device (OLED) of preparing containing embodiment 4, this structure OLED as described in Figure 3.Particularly, the present embodiment OLED the following is glass ITO (100nm)/2-TNATA (60nm)/NPB (20nm)/CBP:8wt%Ir title complex (30nm)/BCP (10nm)/Alq 3(20nm)/Liq (2nm)/Al (100nm).The luminescent layer material of this OLED is two [5-(9 '-carbazyl)-2-(4 ' that prepare doped with 8wt% embodiment 4,6 '-dimethyl) phenyl-1,2,3-benzotriazole-N, C2'] (2,2,6,6-tetramethyl--3,5-heptadione) close the CBP (N of iridium metal complex, two carbazyl-4 of N'-, 4'-dipyridyl).
Know through performance test, the maximum emission wavelength of the electroluminescent spectrum of this device is positioned at 572nm, and maximum current efficiency is 5.24cd/A, and maximum external quantum efficiency is 1.43%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in 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 3, R 4identical or not identical is H or methyl.
2. organic iridium metal complex according to claim 1, is characterized in that: described R 1, R 2, R 3, R 4in arbitrary group be methyl.
3. organic iridium metal complex according to claim 1, is characterized in that: described R 1, R 2, R 3, R 4in any two groups be methyl.
4. a method of preparing the organic iridium metal complex as described in as arbitrary in claim 1～3, comprises the steps:
The compd A of following structural formula general formula is provided;
In the environment of anaerobic, described compd A is carried out to thermal backflow with hydration iridous chloride or the sub-iridium acid of hydration chlorine sodium in reaction solvent and react, generate the chlorine bridge dipolymer B of following structural formula general formula;
In the environment of anaerobic, by described chlorine bridge dipolymer B and 2,2,6,6-tetramethyl--3,5-heptadione carries out thermal backflow reaction in reaction solvent, and purifying obtains organic iridium metal complex of described general formula of molecular structure (I);
Wherein, the R in compd A, compd B general molecular formula 1, R 2, R 3, R 4identical or not identical is H or methyl.
5. the preparation method of organic iridium metal complex according to claim 4, it is characterized in that: in the step of reacting with hydration iridous chloride or the thermal backflow of the sub-iridium acid of hydration chlorine sodium at compd A, described compd A is (2～4) with the mole dosage ratio of hydration iridous chloride or the sub-iridium acid of hydration chlorine sodium: 1.
6. according to the preparation method of the organic iridium metal complex described in claim 4 or 5, it is characterized in that: in the step that compd A and hydration iridous chloride or the thermal backflow of the sub-iridium acid of hydration chlorine sodium are reacted, described reaction solvent is the mixture of 2-methyl cellosolve, cellosolvo, 2 methyl chloride, 3 methyl chloride at least one or 2-methyl cellosolve, cellosolvo, 2 methyl chloride, 3 methyl chloride at least one and distilled water.
7. the preparation method of organic iridium metal complex according to claim 4, it is characterized in that: in described chlorine bridge dipolymer B and 2,2,6,6-tetramethyl--3, in the step of 5-heptadione thermal backflow reaction, described 2,2,6,6-tetramethyl--3,5-heptadione is (2.4～3.2) with the mole dosage ratio of compd B: 1.
8. according to the preparation method of the organic iridium metal complex described in claim 4 or 5, it is characterized in that: in described chlorine bridge dipolymer B and 2,2,6,6-tetramethyl--3, in the step of 5-heptadione thermal backflow reaction, described reaction solvent be 2-methyl cellosolve, cellosolvo, 2 methyl chloride, 3 methyl chloride at least one or 2-methyl cellosolve, cellosolvo, 2 methyl chloride, 3 methyl chloride at least one.
9. the preparation method of organic iridium metal complex according to claim 4, is characterized in that, the preparation method of described compd A is as follows:
By the compound N of following molecular structural formula general formula 0generate compound N through cyclization 1;
By described compound N 1with alkaline metal iodide generation substitution reaction, generate compound N 2;
In the environment of anaerobic, by described compound N 2under alkaline condition, there is substitution reaction with carbazole, generate described compd A;
Wherein, compound N 0, compound N 1and compound N 2r in molecular structural formula general formula 1, R 2, R 3, R 4identical or not identical is H or methyl;
10. the organic iridium metal complex application in organic electroluminescence device, EL cold light film or electrochemical cell luminescent device as electroluminescent phosphorescence material as described in as arbitrary in claim 1～3.
CN201310150560.0A 2013-04-26 2013-04-26 Organic iridium metal complex and preparation method and application thereof Pending CN104119393A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310150560.0A CN104119393A (en) 2013-04-26 2013-04-26 Organic iridium metal complex and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310150560.0A CN104119393A (en) 2013-04-26 2013-04-26 Organic iridium metal complex and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN104119393A true CN104119393A (en) 2014-10-29

Family

ID=51765054

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310150560.0A Pending CN104119393A (en) 2013-04-26 2013-04-26 Organic iridium metal complex and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN104119393A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220123230A1 (en) * 2020-10-20 2022-04-21 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compound and organic electroluminescent device comprising the same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101006161A (en) * 2004-06-28 2007-07-25 西巴特殊化学品控股有限公司 Electroluminescent metal complexes with triazoles and benzotriazoles
CN101631793A (en) * 2007-02-23 2010-01-20 巴斯夫欧洲公司 Electroluminescent metal complexes with benzotriazoles

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101006161A (en) * 2004-06-28 2007-07-25 西巴特殊化学品控股有限公司 Electroluminescent metal complexes with triazoles and benzotriazoles
CN101631793A (en) * 2007-02-23 2010-01-20 巴斯夫欧洲公司 Electroluminescent metal complexes with benzotriazoles

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
TADAS MALINAUSKAS等，: "Multifunctional red phosphorescent bis-cyclometallated iridium complexes based on 2-phenyl-1,2,3-benzotriazole ligand and carbazolyl moieties", 《TETRAHEDRON》, vol. 67, 15 January 2011 (2011-01-15), XP 028365103, DOI: doi:10.1016/j.tet.2011.01.026 *
TOMKUTE-LUKSIENE D.等,: "2-Phenyl-1,2,3-benzotriazole Ir(III) complexes with additional donor fragment for single-layer PhOLED devices", 《DYES AND PIGMENTS》, 23 August 2012 (2012-08-23) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220123230A1 (en) * 2020-10-20 2022-04-21 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compound and organic electroluminescent device comprising the same

Similar Documents

Publication Publication Date Title
CN104119388A (en) Organic iridium metal complex and preparation method and application thereof
CN104119393A (en) Organic iridium metal complex and preparation method and application thereof
CN104119390A (en) Organic iridium metal complex and preparation method and application thereof
CN104140441A (en) Red organic electrophosphorescent material iridium metal complex, preparation method thereof, and organic electroluminescent device
CN104119392A (en) Organic iridium metal complex and preparation method and application thereof
CN104119389A (en) Organic iridium metal complex and preparation method and application thereof
CN104119857A (en) Iridium-metal-complex organic electrophosphorescent material, preparation method thereof and organic electroluminescent device
CN104119391A (en) Organic iridium metal complex and preparation method and application thereof
CN104877664A (en) Blue organic electrophosphorescent material iridium complex and its preparation method and organic electroluminescent device
CN104177434A (en) Red phosphorescence iridium complexes, preparing method thereof and organic electroluminescence device
CN104140446A (en) Red organic electrophosphorescent material iridium metal complex, preparation method thereof, and organic electroluminescent device
CN104140440A (en) Red organic electrophosphorescent material iridium metal complex, preparation method thereof, and organic electroluminescent device
CN104342112A (en) Organic electro-phosphorescent material and preparation method thereof, and organic electroluminescent device
CN104119858A (en) Iridium-metal-complex organic electrophosphorescent material, preparation method thereof and organic electroluminescent device
CN103965251A (en) Red organic electroluminescent material and its preparation method and application
CN103965872A (en) Red organic electroluminescent material and its preparation method and application
CN104177411A (en) Blue electrophosphorescent material iridium metal complex, preparation method and organic electroluminescent device
CN104177410A (en) Blue electrophosphorescent material iridium metal complex, preparation method and organic electroluminescent device
CN104629742A (en) Organic electrophosphorescence material, as well as preparation method and organic electroluminescent device thereof
CN104140442A (en) Red organic electrophosphorescent material iridium metal complex, preparation method thereof, and organic electroluminescent device
CN104629750A (en) Organic electrophosphorescence material, as well as preparation method and organic electroluminescent device thereof
CN104418899A (en) Organic iridium metal complex and preparation method and application thereof
CN104140449A (en) Red organic electrophosphorescent material iridium metal complex, preparation method thereof, and organic electroluminescent device
CN104178114A (en) Red phosphorescence iridium complexes, preparing method thereof and organic electroluminescence device
CN104418898A (en) Organic iridium metal complex and preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20141029