CN102993180A - Dendritic blue light metal complex and application thereof and organic light emitting diode device - Google Patents

Dendritic blue light metal complex and application thereof and organic light emitting diode device Download PDF

Info

Publication number
CN102993180A
CN102993180A CN2012105629400A CN201210562940A CN102993180A CN 102993180 A CN102993180 A CN 102993180A CN 2012105629400 A CN2012105629400 A CN 2012105629400A CN 201210562940 A CN201210562940 A CN 201210562940A CN 102993180 A CN102993180 A CN 102993180A
Authority
CN
China
Prior art keywords
formula
group
blue light
light metal
metal complexes
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.)
Granted
Application number
CN2012105629400A
Other languages
Chinese (zh)
Other versions
CN102993180B (en
Inventor
王利祥
丁军桥
夏德斌
赵磊
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.)
Changchun Institute of Applied Chemistry of CAS
Original Assignee
Changchun Institute of Applied Chemistry of CAS
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 Changchun Institute of Applied Chemistry of CAS filed Critical Changchun Institute of Applied Chemistry of CAS
Priority to CN201210562940.0A priority Critical patent/CN102993180B/en
Publication of CN102993180A publication Critical patent/CN102993180A/en
Application granted granted Critical
Publication of CN102993180B publication Critical patent/CN102993180B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The invention relates to a dendritic blue light metal complex shown by formula (I) and an organic light emitting diode device comprising the dendritic blue light metal complex. A carbazole branch unit in the complex effectively suppresses the gathering of luminous kernels, and excellent hole transport performance of the complex is realized at the same time. An electroluminescence device based on the dendritic blue light metal complex shows the characteristics of low drive voltage, high luminous efficiency and high power efficiency.

Description

Dendroid blue light metal complexes and application thereof and organic light emitting diode device
Technical field
The present invention relates to technical field of organic electroluminescence, relate in particular to dendroid blue light metal complexes and application and organic light emitting diode device.
Background technology
ORGANIC ELECTROLUMINESCENCE DISPLAYS and lighting engineering owing to less energy-consumption, can realize that the plurality of advantages such as large area flexible device have a good application prospect.This technology has been successfully applied to the indicating meter of the electronic products such as part digital camera, mobile phone, mp3 at present.The research-and-development activity of organic electroluminescent mainly concentrates on two aspects: develop high efficiency luminescent material and improve device fabrication.
According to the principle of luminosity of device, electroluminescent organic material can be divided into fluorescent material and phosphor material two large classes.Poor efficiency than organic fluorescence materials, can take full advantage of singlet and triplet excitons in the electroluminescent process based on the phosphor material of transition metal complex, can make in theory the internal quantum efficiency of device reach 100%, therefore phosphor material being used for electroluminescent device becomes the important means that improves material luminous efficiency.For phosphor material, its device preparation technology is generally and it is entrained in the main body itself and the common evaporation of material of main part vacuum.Because this device preparation technology is comparatively complicated, with high costs, limited its application on large-area flat-plate shows.For this reason, develop efficiently, solution processed-type phosphor material seems particularly urgent cheaply.At present, the solution of phosphor material is processed with blend, is chemically bonded in the polymer and three kinds of implementations of dendritic structure.But the above two have some shortcomings: blending method can produce phenomenon of phase separation inevitably; Title complex is incorporated into by chemical bond then has material purifying difficulty in the polymer, polymerization process is brought the problems such as textural defect.
Dendrimer has following characteristics: compound with regular structure forms accurately; Branch can be avoided the luminous cancellation of photophor to there being luminous nucleon that blanketing effect is arranged; Introduce easily functional group; Subject and object is combined together, realize efficient non-doping device.Simultaneously, the introducing of branch can not change electronics and the luminescent properties of intercalated nucleus.Therefore, synthetic dendroid phosphor material is the effective way for preparing the efficient device of low-cost solution processed-type.
Publication number is that the Chinese patent of ZL200710055980.5, ZL200510017140.0 and ZL200710055932.6 discloses ruddiness and the green glow metal complexes of a class take carbazole unit as branch.Because the carbazole branch has good cavity transmission ability, can play the package action to the center luminous nucleon simultaneously, so such phosphor material is very suitable for preparing efficient solution processed-type doping and non-doping device.Wherein, the luminous efficiency of the electroluminescent device of the dendroid phosphor material take the green glow metal iridium complex as luminous nucleon can reach 53.2cd/A; The efficient of the electroluminescent device take the ruddiness metal iridium complex as luminous nucleon then reaches 13.2cd/A.Based on the present situation of carbazole branch metal complexes, it is a kind of take the blue light metal complexes of carbazole branch as the basis that the contriver provides.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of dendroid blue light metal complexes and the application in organic electronic devices and a kind of organic light emitting diode device, makes organic electroluminescence device have higher luminous efficiency, purity of color and power efficiency by the luminescent layer that metal complexes of the present invention is used for organic electroluminescence device.
In view of this, the invention provides a kind of dendroid blue light metal complexes shown in formula I,
Figure BDA00002633801300021
Wherein, M is Ir or Pt;
Q is independently selected from 0 or 1;
When M is Ir, p+q=3, when M is Pt, p+q=2;
Q 1And Q 2Independently be selected from N or CH, and Q 1During for CH, Q 1On hydrogen can be further by R 4Replace;
N is the algebraically of branch unit, is selected from 1,2,3,4 or 5;
R 1And R 2Be independently selected from alkyl, alkoxyl group or the alkylthio of hydrogen, fluorine, cyano group, C1 ~ C40, aryl, aryloxy or the arylthio of C6 ~ C60; Work as R 1And R 2When independently being selected from the alkyl, alkoxyl group of C1 ~ C40 or alkylthio, the hydrogen on the group can be further by one or more R 4Replace; Work as R 1And R 2When independently being selected from the aryl, aryloxy of C6 ~ C60 or arylthio, the hydrogen on the group can be further by one or more R 4Replace;
R 3Be independently selected from the alkyl of hydrogen or C1 ~ C40, work as R 3When independently being selected from the alkyl of C1 ~ C40, one or more hydrogen atoms can be by fluorine, CN or NO 2Substitute, or one or more non-adjacent CH 2Group can be substituted by O or S;
L is linking group, is formula V, formula (VI), and one or more in formula (VII) and formula (VIII) structure:
Wherein, a, b, c, d, e independently are selected from the integer between 1 ~ 10;
Formula V, formula (VI), the hydrogen in formula (VII) and the formula (VIII) can be by R 4Replace;
R 4Be the alkyl of fluorine, cyano group, trifluoromethyl, pentafluoroethyl group, C1 ~ C6 or the alkoxyl group of C1 ~ C6;
X is for having the double dentate anion ligand of 1 ~ 30 carbon atom.
Preferably, described R 3The structure that consists of with described branch unit is a kind of in the following structure:
Figure BDA00002633801300041
R wherein 3Definition cotype (I).
Preferably, described X be single anion part with diketone structure, the double-tooth chelate ligand of single anion with carboxyl or have the double-tooth chelate ligand of the single anion of phenolic hydroxyl group.
Preferably, Q 1For CH and hydrogen can be further by R 4Replace R 1And R 2Be independently selected from fluorine, trifluoromethyl, pentafluoroethyl group, cyano group.
Preferably, Q 1Be N, R 1And R 2Be independently selected from the alkyl of fluorine, trifluoromethyl, pentafluoroethyl group, cyano group, C1 ~ C4, the alkoxyl group, 2 of C1 ~ C4,6-3,5-dimethylphenyl or phenoxy group.
The present invention also provides the application of described dendroid blue light metal complexes in organic electronic devices.
The present invention also provides a kind of organic light emitting diode device, comprise: negative electrode, anode and at least one deck as the organic layer of luminescent layer, it is characterized in that, contain at least a such as each described dendroid blue light metal complexes of claim 1 ~ 5 in the described luminescent layer.
Preferably, described dendroid blue light metal complexes is as the blue light emitting dyestuff in the Organic Light Emitting Diode.
Preferred described Organic Light Emitting Diode is characterized in that, each described dendroid blue light metal complexes of claim 1 ~ 5 is as the material of main part of phosphorescent coloring.
The invention provides blue light metal complexes shown in formula I and preparation method thereof and a kind of organic electroluminescence device.Blue light metal complexes provided by the invention, on the one hand, the dendroid carbazole unit is the gathering of Inhibitory molecules effectively, therefore in the situation of the main consuming body material not, obtain having the non-doped, blue electroluminescent device of greater efficiency, and prepared based on this efficient green and white electroluminescence device; On the other hand, because the introducing of carbazole branch is so that material has excellent hole transport performance, thereby shown low driving voltage, the characteristics of high-luminous-efficiency and high power efficiency based on the electroluminescent device of this dendroid blue light metal complexes.
Description of drawings
Fig. 1 is the organic light emitting diode device structural representation;
Fig. 2 is the graphic representation of brightness-voltage of the organic electroluminescence device of embodiment 10 and Comparative Examples preparation;
Fig. 3 is the graphic representation of luminous efficiency-brightness of the organic electroluminescence device of embodiment 10 and Comparative Examples preparation;
Fig. 4 is the graphic representation of power efficiency-brightness of the organic electroluminescence device of embodiment 10 and Comparative Examples preparation;
Fig. 5 is the luminous intensity-wavelength curve figure of the organic electroluminescence device of embodiment 10 and Comparative Examples preparation.
Fig. 6 is the graphic representation of the current efficiency-power efficiency-brightness of the organic electroluminescence device of embodiment 11 preparation;
Fig. 7 is the graphic representation of the current density-brightness-voltage of the organic electroluminescence device of embodiment 11 preparation;
Fig. 8 is the normalization method electroluminescent spectrum figure of organic electroluminescence device under the 6V driving voltage of embodiment 11 preparations;
Fig. 9 is the graphic representation of the current efficiency-power efficiency-brightness of the organic electroluminescence device of embodiment 12 preparation;
Figure 10 is the graphic representation of the current density-brightness-voltage of the organic electroluminescence device of embodiment 12 preparation;
Figure 11 is the normalization method electroluminescent spectrum figure of organic electroluminescence device under the 6V driving voltage of embodiment 12 preparations.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, but should be appreciated that these describe just as further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of dendroid blue light metal complexes shown in formula I,
Figure BDA00002633801300061
Wherein, M is Ir or Pt;
Q is independently selected from 0 or 1;
When M is Ir, p+q=3, when M is Pt, p+q=2;
Q 1And Q 2Independently be selected from N or CH, and Q 1During for CH, Q 1On hydrogen can be further by R 4Replace;
N is the algebraically of branch unit, is selected from 1,2,3,4 or 5;
R 1And R 2Be independently selected from alkyl, alkoxyl group or the alkylthio of hydrogen, fluorine, cyano group, C1 ~ C40, aryl, aryloxy or the arylthio of C6 ~ C60; Work as R 1And R 2When independently being selected from the alkyl, alkoxyl group of C1 ~ C40 or alkylthio, the hydrogen on the alkyl can be further by one or more R 4Replace; Work as R 1And R 2When independently being selected from the aryl, aryloxy of C6 ~ C60 or arylthio, the hydrogen on the group can be further by one or more R 4Replace;
R 3Be independently selected from the alkyl of hydrogen, C1 ~ C40, work as R 3When independently being selected from the alkyl of C1 ~ C40, one or more hydrogen atoms can be by fluorine, CN or NO 2Substitute, or one or more non-adjacent CH 2Group can be substituted by O or S;
L is linking group, is formula V, formula (VI), and one or more in formula (VII) and formula (VIII) structure:
Wherein, a, b, c, d, e independently are selected from the integer between 1 ~ 10;
Formula V, formula (VI), the hydrogen in formula (VII) and the formula (VIII) can be by R 4Replace;
R 4Be the alkyl of fluorine, cyano group, trifluoromethyl, pentafluoroethyl group, C1 ~ C6 or the alkoxyl group of C1 ~ C6;
X is for having the double dentate anion ligand of 1 ~ 30 carbon atom.
Described R 3The structure optimization that consists of with described branch unit is a kind of in the following structure:
Figure BDA00002633801300072
Figure BDA00002633801300081
R 3Be surface group, its the position of substitution on the carbazole unit preferably on two phenyl ring at carbazole unit symmetrical position replace, preferredly replace and in the situation of 2 and 7 replacements of carbazole at 3 of carbazole unit and 6, most preferably in 3 and 6 replacements of carbazole.
R 3Hydrogen more preferably, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, the 2-methyl butyl, n-pentyl, sec.-amyl sec-pentyl secondary amyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, suberyl, n-octyl, the ring octyl group, the 2-ethylhexyl, trifluoromethyl, pentafluoroethyl group, 2,2,2-trifluoroethyl, methoxyl group, oxyethyl group, the 2-methoxy ethoxy, the 2-ethoxy ethoxy, (2-methoxy ethoxy) oxyethyl group, (2-ethoxy ethoxy) oxyethyl group, 2-methylmercaptan ethyl sulfenyl, 2-ethylmercapto group ethylmercapto group, (2-methylmercaptan ethyl sulfenyl) ethylmercapto group or (2-ethylmercapto group ethylmercapto group) sulfenyl.R 3Most preferably be hydrogen, methyl, ethyl, the tertiary butyl, methoxyl group, oxyethyl group, 2-methoxy ethoxy, 2-ethoxy ethoxy, (2-methoxy ethoxy) oxyethyl group or (2-ethoxy ethoxy) oxyethyl group.
L is for connecting the group of branch unit and centronucleus, and described L is formula V, formula (VI), and one or more in formula (VII) and formula (VIII) structure, concrete, described L can be formula (V), formula VI, formula (VII) or formula (VIII) etc.; The combination of formula (V) and formula VI, combination of formula VI and formula (VII) etc.; The combination of formula (V), formula VI and formula (VII), combination of formula VI formula (VII) and formula (VIII) etc.;
Figure BDA00002633801300082
A, b, c, d, e independently are selected from the integer between 1 ~ 10, formula V, formula (VI), the hydrogen in formula (VII) and the formula (VIII) can be by R 4Replace.
Described linking group L is formula V more preferably, formula (VI), one or both in formula (VII) and formula (VIII) structure, a, b, c, d independently are preferably the integer between 1 ~ 5, formula (VII) and (VIII) in H on the CH can be by methyl substituted.
Described L the position of substitution on the pyridine unit of part be preferably coordination N atom between the position and contraposition.
The double-tooth chelate ligand of the single anion that described X is preferably single anion part with diketone structure, have carboxyl or have the double-tooth chelate ligand of the single anion of phenolic hydroxyl group.X is acetyl acetone ligands more preferably, pyridine carboxylic acid part, hexafluoroacetylacetone part, salicylic aldehyde part, oxine part, amino acid ligand, quadrol part, phenylpyridine part, benzoxazole part, the benzothiazole part, benzoglyoxaline part, thionaphthene part, phenylquinoline part.Most preferred, X is acetyl acetone ligands and pyridine carboxylic acid part.
As preferred version, Q in the described dendroid blue light metal complexes 1When being preferably CH, hydrogen wherein can be further by R 4Replace R 1And R 2Be independently selected from fluorine, trifluoromethyl, pentafluoroethyl group, cyano group.
According to the present invention, Q 1When being preferably N, R 1And R 2Be independently selected from fluorine, trifluoromethyl, pentafluoroethyl group, cyano group, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, tert.-butoxy, alkoxyl group, 2,6-3,5-dimethylphenyl or phenoxy group
R4 is preferably fluorine, cyano group, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, methoxyl group, oxyethyl group, propoxy-or isopropoxy.
As preferred version, the example of the dendroid blue light metal complexes shown in formula I is as follows:
Figure BDA00002633801300101
Figure BDA00002633801300111
Figure BDA00002633801300121
The preparation method of the dendroid blue light metal complexes shown in the formula I may further comprise the steps:
Will be suc as formula part and the IrCl shown in (I X) 33H 2O or K 2PtCl 4In solvent, react, obtain chlorine bridge precursor;
Under the effect of catalyzer, described chlorine bridge precursor and the part with formula (I X) structure are carried out coordination reaction in solvent, obtain the metal complexes shown in formula I;
Figure BDA00002633801300131
In the process of metal complexes of preparation shown in formula I, at first carried out the synthetic of chlorine bridge precursor, described preparation method the present invention suc as formula the part shown in (I X) has no particular limits, and gets final product according to the preparation method of prior art.Described solvent is this area solvent commonly used, and the present invention is preferably the mixed solvent of ethylene glycol monomethyl ether and water, and the volume ratio of described ethylene glycol monomethyl ether and water is preferably 1 ~ 5:1.In order to improve the solvability of part, the present invention preferably adds the first solvent, and described the first solvent is preferably tetrahydrofuran (THF) or dioxane, and the volume of described the first solvent accounts for 1% ~ 50% of solvent and the first solvent cumulative volume.The temperature of described reaction is preferably 80 ~ 140 ℃, and more preferably 100 ~ 120 ℃, the time of described reaction is preferably 8 ~ 72h, more preferably 15 ~ 36h.
After above-mentioned chlorine bridge precursor preparation is finished, described chlorine bridge precursor and the part shown in (I X) are carried out coordination reaction, thereby obtain the metal complexes shown in (I).The temperature of described coordination reaction is preferably 80 ~ 240 ℃, and more preferably 120 ~ 200 ℃, the time of described coordination reaction is preferably 8 ~ 72h, more preferably 20 ~ 36h.Described catalyzer is preferably basic cpd, more preferably Na 2CO 3Or AgSO 3CF 3Described solvent is preferably alcohol derivatives, more preferably ethylene glycol monomethyl ether, ethylene glycol monoemethyl ether or glycerine.Same in order to improve the solvability of chlorine bridge precursor and part, the present invention preferably adds the second solvent, described the second solvent is preferably glycol ether, Triethylene glycol, tetraethylene-glycol or chloroform, and the volume of described the second solvent preferably accounts for 1% ~ 50% of solvent and the second solvent cumulative volume.
According to the present invention, after described coordination reaction is finished, further comprising the steps of: as the product after the coordination reaction and solvent to be shone under UV-light, obtain the metal complexes shown in formula I.Described ultraviolet wavelength is preferably 250 ~ 400nm, more preferably 365nm; The described ultraviolet irradiation time is preferably 4 ~ 24h, more preferably 10 ~ 18h; Described solvent is preferably methylene dichloride.
The invention still further relates to the application of dendroid blue light metal complexes on organic electronic devices of such scheme.Described organic electronic devices includes but not limited to organic field effect tube (OFET), thin film transistor (TFT), unicircuit (IC), RFID tag, photo-detector, sensor, logical circuit, storage element, electrical condenser, organic photovoltaic battery (OPV), schottky diode, antistatic film, conductive base material or pattern, polymer dielectric film (PEM), organic optical dioptric device, optical conductor, electrophotographic member, field quenching device, organic light-emitting transistor (OLET), Organic Light Emitting Diode (OLED), polymer LED (PLED) and organic laser diode.Described dendroid blue light metal complexes is the application in Organic Light Emitting Diode (OLED) and polymer LED (PLED) especially.
The present invention also provides a kind of organic light emitting diode device, and described organic light emitting diode device comprises: anode, negative electrode and at least one deck comprise at least a dendroid blue light metal complexes in the described organic luminous layer as the organic layer of luminescent layer.
As shown in Figure 1, Fig. 1 is the structure of the preferred organic electroluminescence device of the present invention, and the structure of the organic electroluminescence device among Fig. 1 is substrate 101, the first electrode 102, hole injection layer 103, luminescent layer 104, hole blocking layer 105, electron transfer layer 106, electron injecting layer 107 and the second electrode 108 that successively stack arranges.Must be pointed out hole injection layer 103, hole blocking layer 105, electron transfer layer 106, electron injecting layer 107 nonessential existence.And for further optimised devices efficient, can also introduce hole transmission layer, electronic barrier layer between hole injection layer and the luminescent layer.The thickness of above-mentioned each layer is selected according to thickness well known to those skilled in the art.
That the material of described substrate 101 is preferably is transparent, be easy to process and the plastic of the glass substrate of waterproof and surface uniform or transparent flexibility.
Described the first electrode 102 preferably is made of the conducting metal that is easy to inject in the hole or the metal oxide of conduction, the material of described the first electrode 102 is indium tin oxide (ITO), indium-zinc oxide (IZO), nickel (Ni), platinum (Pt) or gold (Au) more preferably, and highly preferred is indium tin oxide (ITO).
The material of hole injection layer 103 is preferably the mixture of water miscible poly-(3,4-Ethylenedioxy Thiophene) and poly styrene sulfonate.
Luminescent layer 104 comprises described dendroid blue light metal complexes.
Described dendroid blue light title complex is preferably as blue phosphorescence luminescent dye, directly consists of luminescent layer 104 with the form of non-doping; Can also be prepared with organic electroluminescent layer with the form that material of main part mixes.The present invention selects according to material well known to those skilled in the art described material of main part.
Described dendroid blue light title complex also can be used as material of main part, is mixed with luminescent layer with phosphorescent coloring.The present invention does not have particular restriction to described phosphorescent dopants, is preferably ordination number and is the compound of 25 ~ 86 element, and more preferably ordination number is the compound of 56 ~ 80 element, more preferably iridic compound.The percentage composition that the described dendroid blue light of technique scheme title complex occupies organic electroluminescent layer is preferably 99wt% ~ 1wt%, 99wt% ~ 5wt% more preferably, most preferably be 99wt% ~ 70wt%, the percentage composition that described phosphorescent dopants occupies organic electroluminescent layer is preferably 1wt% ~ 99wt%, more preferably 1wt% ~ 95wt% most preferably is 1wt% ~ 30wt%.
The material of described hole blocking layer 105 is preferably the phenanthroline derivative, and more preferably 2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline (BCP), pyridine derivate, triphenyl phosphorus oxygen derivative, oxadiazole derivative or aluminium complex.
The material of described electron transfer layer 106 is preferably pyridine derivate, triphenylphosphine oxide derivative, oxazole derivative, oxadiazole derivative, Isoxazole derivative, triazole derivative, thiadiazoles derivative, imdazole derivatives or aluminium complex.
The material of described electron injecting layer 107 is preferably LiF, NaCl, NaOH, CsF, Cs 2CO 3Or Ca(acac) 2
The material of described the second electrode 108 is preferably low work function metal, more preferably Ca, Ba, Al, Mg or Ag.
The present invention does not have particular restriction to the preparation method of described organic electroluminescence device, can carry out in accordance with the following methods:
In the described organic electroluminescence device process of preparation, at first form the first electrode 102 of pattern words at substrate 101, the present invention does not have particular restriction to generation type, gets final product according to method well known to those skilled in the art, also can use business-like product.
After obtaining the first electrode 102, form hole injection layer 103 at described anode.Can pass through solution spin coating, ink jet printing, offset printing or stereosopic printing forms at described the first electrode 102.
After obtaining the first electrode 103, described luminescent layer 104 can pass through solution spin coating, ink jet printing, offset printing or stereosopic printing and form at described the first electrode 103.The solvent of selecting is preferably toluene, dimethylbenzene, chlorobenzene, dichlorobenzene and trichlorobenzene solvent, more preferably toluene, chlorobenzene, dichlorobenzene solvent.
After described organic luminous layer formed, the mode by vacuum evaporation, solution spin coating, ink jet printing, offset printing or stereosopic printing formed hole blocking layer 105 and electron transfer layer 106 and electron injecting layer 107 successively in its surface.
After obtaining electronic injection/transport layer, form the second electrode 108 thereon, can obtain organic electroluminescence device.The present invention does not have particular restriction to generation type, is preferably method well known to those skilled in the art, includes but not limited to vacuum moulding machine.Described negative electrode preferable alloy includes but not limited to calcium, magnesium, barium, aluminium and silver, is preferably aluminium.
In order further to understand the present invention, below in conjunction with embodiment dendroid blue light metal complexes provided by the invention is elaborated, protection scope of the present invention is not limited by the following examples.
Embodiment 1 Compound I 1Synthetic
D1Bu's is synthetic
In reaction flask, add Isosorbide-5-Nitrae-dibromobutane (5ml, 46.24mmol), TBAB(0.23g, 1.2mmol under the condition of ice bath), benzene (7ml), 50% sodium hydroxide.Add di-t-butyl carbazole (2.0g, 11.56mmol), reaction is 1.5 hours under the ice bath in batches, and the recession deicing was bathed in 6 hours, at room temperature reacted stopped reaction after about 10 hours, and column chromatography for separation obtains D1BuBr.The productive rate of D1BuBr is 54%.Product D 1BuBr is carried out nuclear magnetic resonance spectroscopy, and characterization result is as follows: 1H NMR(300MHz, CDCl3) [ppm]: δ 8.10(s, 2H), 7.51(d, J=8.5,2H) and, 7.29(d, J=8.7,2H), 4.29(t, J=6.6Hz, 2H), 3.38(t, J=6.2Hz, 2H), 2.00-2.10(m, 2H), 1.90-1.97(m, 2H) and, 1.46(s, 18H).
D1BuOPyBr's is synthetic
Disubstituted-4-hydroxy-2 bromopyridine (0.98g, 5.59mmol) is added to 25ml acetone makes it entirely molten, adds Anhydrous potassium carbonate (3.9g, 28.3mmol), and stirring adds D1Bu(2.45g, 5.59mmol after half hour).Back flow reaction 20 hours, stopped reaction, quiet to room temperature.Suction filtration, filter cake is used anhydrous magnesium sulfate drying with twice of dichloromethane extraction with filtrate mixing afterwards with water-soluble, suction filtration, filtrate is revolved steaming, then uses sherwood oil: ethyl acetate=10:1 column chromatography for separation obtains product D 1BuOPyBr, and the productive rate of D1BuOPyBr is 82%.Product D 1BuOPyBr is carried out nuclear magnetic resonance spectroscopy, and characterization result is as follows: 1H NMR(300MHz, CDCl3) [ppm]: δ 8.12(s, 2H), 8.13(d, J=5.8,1H), 7.48(d, J=0.9,4H), 7.17(d, J=2.2,1H), 6.96(dd, J=2.2,5.8Hz 1H), 4.40(t, J=6.7Hz, 2H), 4.01(t, J=6.4Hz, 2H), 1.84-1.92(m, 2H), 1.67-1.76(m, 2H), 1.40(s, 18H).
D1BuOPyPhF 2Synthetic
D1BuOBrPy(1.0g, 2.0mmol), 2,4-difluorobenzene boric acid (0.32g, 2.0mmol) TBAB(0.09g, 0.2mmol), substitute gas three times, catalyzer is put vacuum nitrogen filling gas in the bottle of the sharp end of a lucifuge, then with injection system after the toluene dissolving, 2M salt of wormwood (aq) injects reaction system after removing oxygen.Reaction is 60 hours under the 90 degrees centigrade of lucifuges that heat up, stopped reaction.Filter, salt deposit merges drying with using dichloromethane extraction after the water dissolution with filtrate, then filters concentrated solvent.Take the solvent of sherwood oil: ethyl acetate=10:1 as eluent carries out column chromatography for separation, obtain product D 1BuOPyPhF 2D1BuOPyPhF 2Productive rate be 53%.To D1BuOPyPhF 2Product carries out nuclear magnetic resonance spectroscopy, and characterization result is as follows: 1H NMR(300MHz, CDCl3) [ppm]: δ 8.47(d, J=5.7Hz, 1H), 8.18(s, 2H), 7.90-7.99(m, 1H), 7.45-7.51(m, 4H), 7.37(ddd, J=2.5,9.4,11.6Hz3H), 7.17-7.23(m, 2H), 6.95(dd, J=2.3,5.7Hz, 1H), 4.41(t, J=6.4Hz, 2H), 4.1(t, J=6.1Hz, 2H), 1.88-1.95(m, 2H), 1.68-1.80(m, 2H), 1.40(s, 18H).
Synthesizing of chlorine bridge precursor 2
With ligand 1 (0.5937g, 1.1mmol) and IrCl 33H 2O(0.3038g, 0.5mmol) add in 12mL ethylene glycol monomethyl ether and the 4mL distilled water, stirring heating under argon shield behind the back flow reaction 48h, leaves standstill to room temperature, adds water to without precipitation to occur, suction filtration, 50 degrees centigrade in filter cake vacuum is drained, and obtains chlorine bridge precursor 2.
Compound I 1Synthetic
With chlorine bridge precursor 2(0.6371g; 0.415mmol), ligand 1 (0.4511g; 0.83mmol), silver trifluoromethanesulfonate (0.2223g; 0.87mmol), Anhydrous potassium carbonate (0.28g; 2.1mmol) add in the 50ml round-bottomed flask with sym-trimethylbenzene (8ml); under argon shield, be warming up to backflow, reacted 72 hours.Cool to room temperature filters, and filter cake is washed with methylene dichloride, and the concentrated rear pillar of filtrate separates to get product GB-D1.Product is carried out nuclear magnetic resonance spectroscopy, and characterization result is as follows: 1H NMR(300MHz, CDCl 3): δ 8.09(t, J=1.7Hz, 6H), 7.72(t, J=2.7Hz, 3H), 7.45(dd, J=1.9,8.6Hz, 6H), 7.29(d, J=8.6Hz, 6H), 7.20(d, J=6.4Hz, 3H), 6.30-6.39(m, 6H), 6.28(dd, J=2.2,9.1Hz, 3H), 4.33(t, J=6.6Hz, 6H), 4.00(t, J=5.8Hz, 6H), 2.01-2.10(m, 6H), 1.80-1.89(m, 6H), 1.44(s, 54H).Compound I 1Building-up process be shown below:
Figure BDA00002633801300181
Embodiment 2 Compound I 2Synthetic
D2Bu's is synthetic
Add 1 in the single port bottle, 4-dibromobutane (4ml, 33.2mmol), TBAB(0.3g, 0.92mmol), benzene (9ml) and 50% sodium hydroxide (9ml), begin to stir, add two generation carbazoles (4.0g, 5.54mmol) in batches, finished in about 1.5 hours, and at room temperature reacted about 12 hours stopped reaction.Use dichloromethane extraction, anhydrous sodium sulfate drying, suction filtration is spin-dried for filtrate, and then column chromatography for separation gets product D 2Bu, and eluent is sherwood oil.The productive rate 63% of D2Bu.Product is carried out nuclear magnetic resonance spectroscopy, and characterization result is as follows: 1H NMR(300MHz, CDCl3) [ppm]: δ 8.55(d, 1.8Hz2H), 8.29(d, J=1.5Hz4H), 7.98(d, 8.7Hz2H), 7.69(dd, J=1.9,8.7Hz, 2H), 7.46(dd, J=1.8,8.7Hz, 4H), 7.29(d, J=8.6Hz, 4H), 4.66(br, 2H), 3.68(t, J=5.7Hz, 2H), 2.06(br, 4H), 1.41(s, 36H).
D2BuOPyBr's is synthetic
Disubstituted-4-hydroxy-2 bromopyridine (0.52g, 3mmol) adds acetone (20ml) makes it entirely molten, adds Anhydrous potassium carbonate (2.07g, 15mmol), and stirring adds D2BuBr(2.57g, 3mmol after half hour).The stopped reaction after 20 hours that refluxes, quiet to room temperature.Suction filtration, filter cake is used anhydrous magnesium sulfate drying with twice of dichloromethane extraction with filtrate mixing afterwards with water-soluble, suction filtration, filtrate is revolved steaming, and then using sherwood oil: ethyl acetate=10:1 is that the eluent column chromatography for separation obtains product D 2BuOPyBr.The productive rate 69% of D2BuOPyBr.Product is carried out nuclear magnetic resonance spectroscopy, and characterization result is as follows: 1H NMR(300MHz, CDCl3) [ppm]: δ 8.56(s, 2H), 8.29(s, 4H) and, 8.17(dd, 0.8,5.7Hz1H), 7.98(d, J=8.6Hz, 2H), 7.69(d, J=8.7Hz, 2H), 7.46(d, J=8.7Hz, 4H), 7.28(d, J=8.9Hz, 5H), 7.04(m, 1H), 4.68(t, J=5.8Hz, 2H), 4.21(t, J=5.9Hz, 2H), 2.05-2.11(m, 2H), 1.90-1.99(m, 2H), 1.41(s, 36H).
Synthesizing of part 3
With D2BuOBrPy(0.48g, 0.5mmol), 2,4-difluorobenzene boric acid (0.15g, 1mmol) TBAB, take a breath three times, tetra-triphenylphosphine palladium (0.02g, 0.017mol) is put vacuum nitrogen filling gas in the bottle of the sharp end of a lucifuge, then with injection system after the toluene dissolving, 2M salt of wormwood (aq) (0.55ml) injects reaction system after removing oxygen.Reaction is 60 hours under the 90 degrees centigrade of lucifuges that heat up, stopped reaction.Filter, salt deposit merges drying with using dichloromethane extraction after the water dissolution with filtrate, then filters, and revolves desolventizing.Take the solvent of sherwood oil: ethyl acetate=5:1 as eluent carries out column chromatography for separation, obtain part 3.The productive rate of part 3 is 55%.Product is carried out nuclear magnetic resonance spectroscopy, and characterization result is as follows: 1H NMR(300MHz, CDCl 3): δ 8.55(d, 1.9Hz2H), 8.49(d, J=5.7Hz1H) and, 8.28(d, 1.6Hz4H), 7.94-7.99(m, 3H), 7.67(dd, J=1.9,8.7Hz, 2H), 7.26-7.35(m, 6H), 7.18(ddd, J=2.4,8.5,8.6Hz, 1H), 7.01(dd, J=2.4,5.7Hz, 1H), 4.69(t, J=6.2Hz, 2H), 4.22(t, J=6.1Hz, 2H), 2.10-2.15(m, 2H), 1.95-2.01(m, 2H), 1.41(s, 36H).
Synthesizing of chlorine bridge precursor 4
With part 3(0.4326g, 0.44mmol) and IrCl 33H 2O(0.071g, 0.2mmol) be added in 7.5mL ethylene glycol monomethyl ether, 4.5mL distilled water and the 6mL tetrahydrofuran (THF) stirring heating under argon shield; behind the back flow reaction 48h, leave standstill to room temperature, add water to without the precipitation appearance; suction filtration, 50 degrees centigrade in filter cake vacuum are drained, and obtain chlorine bridge precursor 4.
Compound I 2Synthetic
With chlorine bridge precursor 4(0.4913g; 0.2035mmol), part 3(0.4069g; 0.4001mmol), silver trifluoromethanesulfonate (0.1147g; 0.4477mmol), Anhydrous potassium carbonate (0.1410g; 1.0175mmol) and sym-trimethylbenzene (15ml), add in the 50ml round-bottomed flask, under argon shield; be warming up to backflow, reacted 72 hours.Cool to room temperature filters, and filter cake is washed with methylene dichloride, and the concentrated rear pillar of filtrate separates to get product I2, the productive rate 26% of I2.Product is carried out nuclear magnetic resonance spectroscopy, and characterization result is as follows: 1H NMR(300MHz, CDCl 3): δ 8.18(s, 6H), 8.14(d, J=1.2Hz12H) and, 7.79(br, 3H), 7.63(m, 12H), 7.41(dd, J=1.7,8.6Hz, 12H), 7.28(d, J=8.7Hz2H), 6.42(dd, J=2.1,6.2Hz, 3H), 6.34(ddd, J=2.0,8.9,11.6Hz, 3H), 6.24(dd, J=2.1,9.0Hz, 3H), 4.54(t, J=6.6Hz, 6H), 4.1(t, J=5.4Hz, 6H), 2.20-2.27(m, 6H), 1.96-2.03(m, 6H), 1.44(s, 108H).I 2Building-up process be shown below:
Figure BDA00002633801300211
Embodiment 3 Compound I 4Synthetic
Synthesizing of part 5
In there-necked flask, add D1BuOPyBr(2.81g, 5.5mmol), TBAB(0.18g, 0.55mmol), 2,6-difluoro pyridine boric acid (0.97g, 6.1mmol), add 2M solution of potassium carbonate (10ml), THF dissolving tetra-triphenylphosphine palladium (0.32g, 0.28mmol) injects the system that has extracted oxygen.Heat 90 ℃ of back flow reaction 32h.Use dichloromethane extraction, anhydrous sodium sulfate drying, suction filtration is spin-dried for filtrate, and column chromatography for separation gets product, and eluent is crossed out top raw material point with PE:EA=8:1, then filters out product part 5 with PE:EA=4:1.The productive rate 62% of part 5.Product is carried out nuclear magnetic resonance spectroscopy, and characterization result is as follows: 1H NMR(300MHz, CDCl3): δ 8.68(dd, J=8.3,17.3Hz, 1H), 8.49(d, J=5.8Hz, 1H), 8.10(d, J=1.6Hz, 2H), 7.52(dd, J=1.6,8.5Hz, 2H), 7.31-7.33(m, 3H), 7.00(dd, J=2.0,5.8Hz, 1H), 6.75(dd, J=2.9,8.2Hz, 1H), 4.36(t, J=6.7Hz, 2H), 4.02(t, J=6.1Hz, 2H), 2.05-2.14(m, 2H), 1.85-1.95(m, 2H), 1.46(s, 18H).
Synthesizing of chlorine bridge precursor 6
With part 5(0.6g, 1.11mmol) and IrCl 33H 2O(0.1953g, 0.55mmol) add in 12mL ethylene glycol monomethyl ether and the 4mL distilled water, stirring heating under argon shield behind the back flow reaction 48h, leaves standstill to room temperature, adds water to without precipitation to occur, suction filtration, 50 degrees centigrade in filter cake vacuum is drained, and obtains chlorine bridge precursor 6.
Compound I 4Synthetic
With chlorine bridge precursor 6(0.64g; 0.42mmol), part 5(0.45g; 0.84mmol), silver trifluoromethanesulfonate (0.24g; 0.92mmol), Anhydrous potassium carbonate (0.3g; 2.1mmol), sym-trimethylbenzene (12ml), add in the 50ml round-bottomed flask, under argon shield; be warming up to backflow, reacted 72 hours.Cool to room temperature, reaction solution directly separate to get solid through post, place under the 365nmUV irradiation 12h to get product B B-D1, BB-D1 productive rate 15% this solid.Product is carried out nuclear magnetic resonance spectroscopy, and characterization result is as follows: 1H NMR(300MHz, CDCl 3): δ 8.09(d, J=1.62Hz, 6H), 7.72(s, 3H), 7.5(dd, J=1.8,8.6Hz, 6H), 7.29(d, J=8.6Hz, 6H), 7.17(d, J=6.2,3H), 6.44(d, J=4.5Hz, 3H), 4.34(t, J=6.5Hz, 6H), 4.01(t, J=5.5Hz, 6H), 2.02-2.12(m, 6H), 1.85-1.90(m, 6H), 1.44(s, 54H).I 4Building-up process formula specific as follows shown in:
Figure BDA00002633801300221
Embodiment 4 Compound I 5Synthetic
Synthesizing of part 7
Add D2BuOPyBr(4.83g in the there-necked flask, 5.08mmol), TBAB(0.16g, 0.51mmol), 2,6-difluoro pyridine boric acid (1.21g, 7.62mmol), add 2M solution of potassium carbonate (10ml), THF dissolving tetra-triphenylphosphine palladium (0.29g, 0.25mmol) injects the system of deoxygenation.Heat 90 ℃ of back flow reaction 12h stopped reaction.Use dichloromethane extraction, anhydrous sodium sulfate drying, suction filtration is spin-dried for filtrate, and column chromatography for separation gets product, and eluent is that PE:DCM=1:1 filters out product part 7.The productive rate 60% of part 7.Product is carried out nuclear magnetic resonance spectroscopy, and characterization result is as follows: 1H NMR(300MHz, CDCl3) [ppm]: δ 8.68(dd, J=8.1,17.3Hz, 1H), 8.53(d, J=5.8Hz, 1H), 8.19(s, 2H), 8.16(d, J=1.5Hz, 4H), 7.66(s, 4H), 7.45(dd, J=1.7,8.7Hz, 4H), 7.40(s, 1H), 7.31(d, J=8.6Hz, 4H), 6.95(t, dd=2.9,8.2Hz, 1H), 6.83(dd, J=2.1,5.7Hz, 1H), 4.61(t, J=6.7Hz, 2H), 4.17(t, J=5.9Hz, 2H), 2.25-2.35(m, 2H), 2.03-2.12(m, 2H), 1.46(s, 36H).
Synthesizing of chlorine bridge precursor 8
With part 7(1.3g, 1.3208mmol) and IrCl 33H 2O(0.2326g, 0.6604mmol) add in 25mL ethylene glycol monomethyl ether, 7mL distilled water and the 25mL tetrahydrofuran (THF) stirring heating under argon shield; behind the back flow reaction 48h, leave standstill to room temperature, add water; use the dichloromethane extraction water, obtain 0.4315g chlorine bridge precursor 8 after the organic phase desolventizing.
Compound I 5Synthetic
With chlorine bridge precursor 8(0.9486g; 0.2161mmol), part 7(0.4677g; 0.4754mmol), silver trifluoromethanesulfonate (0.1218g; 0.4754mmol), Anhydrous potassium carbonate (0.1498g; 1.0805mmol), sym-trimethylbenzene (40ml), add in the 50ml round-bottomed flask, under argon shield; be warming up to backflow, reacted 72 hours.Cool to room temperature, reaction solution directly separate to get solid through post, place under the 365nmUV irradiation 12h to get product I this solid 13, the productive rate 20% of BB-D2.Product is carried out nuclear magnetic resonance spectroscopy, and characterization result is as follows: 1H NMR(300MHz, CDCl 3): δ 8.20(s, 6H), 8.16(s, 12H) and, 8.19(s, 2H), 7.81(s, 3H), 7.62(s, 12H), 7.42(d, J=8.5Hz, 12H), 7.29(d, J=8.5Hz, 12H), 7.23(s, 3H), 6.55(br, 3H), 6.19(s, 3H), 4.55(br, 6H), 4.13(m, 6H), 2.27(br, 6H), 2.04(m, 6H), 1.46(s, 108H).
Figure BDA00002633801300241
Embodiment 5 Compound I 10Synthetic
With chlorine bridge precursor 2(0.64g, 0.42mmol), pyridine carboxylic acid (0.11g, 0.83mmol), yellow soda ash (0.44g; 4.2mmol), ethylene glycol monomethyl ether (20ml), chloroform (10ml) add in the 50ml round-bottomed flask; under argon shield, be warming up to backflow, reacted 24 hours.The removal of solvent under reduced pressure rear pillar separates to get product GB-D1-Pic, productive rate 80%.Product is carried out nuclear magnetic resonance spectroscopy, and characterization result is as follows: 1H NMR(400MHz, CDCl 3): δ 8.44(d, J=6.67Hz, 1H), 8.30(d, J=7.77Hz, 1H), 8.10(s, 4H), 7.90(t, J=7.67Hz, 1H), 7.75(d, J=7.77Hz, 1H), 7.72(t, J=3.03Hz, 1H), 7.65(br, 1H), 7.52(d, J=8.55Hz, 4H), 7.38(d, J=6.80Hz, 1H), 7.34(d, J=4.14Hz, 2H), 7.32(d, J=4.14Hz, 2H), 7.12(d, J=6.69Hz, 1H), 6.65(dd, J=2.44, J=6.60Hz, 1H), 6.33-6.46(m, 3H), 5.86(dd, J=2.21, J=8.71Hz, 1H), 5.62(dd, J=2.15, J=8.71Hz, 1H), 4.35-4.39(m, 4H), 4.03-4.07(m, 4H), 2.09-2.12(m, 4H), 1.88-1.92(m, 4H), 1.45(s, 36H).I 7Building-up process be shown below:
Figure BDA00002633801300251
Embodiment 6I 10Synthetic
With chlorine bridge precursor 6(0.64g, 0.42mmol), pyridine carboxylic acid (0.11g, 0.83mmol), yellow soda ash (0.44g; 4.2mmol), ethylene glycol monomethyl ether (20ml) and chloroform (10ml) add in the 50ml round-bottomed flask; under argon shield, be warming up to backflow, reacted 24 hours.The removal of solvent under reduced pressure rear pillar separates to get product B B-D1-Pic.Product is carried out nuclear magnetic resonance spectroscopy, and characterization result is as follows: 1H NMR(400MHz, CDCl 3): δ 8.38-8.46(m, 1H), 8.27-8.33(m, 1H) and, 8.11(s, 4H), 7.92-7.99(m1H), 7.71-7.76(m, 2H), 7.65(s, 1H), 7.52(d, J=8.46Hz, 4H), 7.38-7.47(m, 1H), 7.32(dd, J=3.86,8.47Hz, 4H), 7.07-7.15(m, 1H), 6.64-6.74(m, 1H), 6.41-6.51(m, 1H), 5.86(s, 1H), 5.62(d, J=11.62Hz, 1H), 4.37(m, 4H), 4.08(br, 4H), 2.09-2.12(m, 4H), 1.89-1.91(m, 4H), 1.45(s, 36H).Product I 10Preparation process be shown below:
The material of main part H2 that adopts in following examples, the structure of electron transport material DPSF and contrast blue light complex of iridium FIrpic is as follows:
Embodiment 7
Adopt I 2The electroluminescent device that assembling is mixed, the structure of device is: ITO/PEDOT(40nm)/H2:10wt%I 2(40nm)/DPSF(50nm)/LiF(1nm)/Al(100nm).The packaging technology of device is as follows:
After conducting polymer polythiofuran derivative (PEDOT) is spin-coated on the ito glass surface of cleaning in advance with 3000 rev/mins speed, at 120 ℃ of lower baking 30min, forms the thick hole of 50nm and inject two-layer electrode, and improve the planarization on ito glass surface; With 1mg I 2Be dissolved in the chlorobenzene with 9mgH2, be made into the solution of 10 mg/ml, it is upper as luminescent layer to be spin-coated on PEDOT with 1500 rev/mins speed; Under the condition of vacuum, the DPSF that evaporation 50nm is thick on luminescent layer is as electron transfer layer, subsequently successively evaporation LiF and Al electrode.
The experiment structure shows: the bright voltage that opens of El element is 4.6V, and maximum luminous efficiency is 12.7cd/A, and maximum power efficiency is 8.5lm/W, high-high brightness 3000cd/m 2, chromaticity coordinates CIE value x=0.16, y=0.29.
Embodiment 8
Adopt I 2The electroluminescent device that assembling is mixed, the structure of device is: ITO/PEDOT(40nm)/H2:20wt%I 2(40nm)/DPSF(50nm)/LiF(1nm)/Al(100nm).The packaging technology of device is as follows:
After conducting polymer polythiofuran derivative (PEDOT) is spin-coated on the ito glass surface of cleaning in advance with 3000 rev/mins speed, at 120 ℃ of lower baking 30min, forms the thick hole of 50nm and inject two-layer electrode, and improve the planarization on ito glass surface; 2mg I2 and 8mg H2 are dissolved in the chlorobenzene, are made into the solution of 10 mg/ml, it is upper as luminescent layer to be spin-coated on PEDOT with 1500 rev/mins speed; Under the condition of vacuum, the DPSF that evaporation 50nm is thick on luminescent layer is as electron transfer layer, subsequently successively evaporation LiF and Al electrode.
The experiment structure shows: the bright voltage that opens of El element is 3.8V, and maximum luminous efficiency is 13.7cd/A, and maximum power efficiency is 10.7lm/W, high-high brightness 3700cd/m 2, chromaticity coordinates CIE value x=0.15, y=0.23.
Embodiment 9
Adopt I 2The electroluminescent device that assembling is mixed, the structure of device is: ITO/PEDOT(40nm)/H2:30wt%I 2(40nm)/DPSF(50nm)/LiF(1nm)/Al(100nm).The packaging technology of device is as follows:
After conducting polymer polythiofuran derivative (PEDOT) is spin-coated on the ito glass surface of cleaning in advance with 3000 rev/mins speed, at 120 ℃ of lower baking 30min, forms the thick hole of 50nm and inject two-layer electrode, and improve the planarization on ito glass surface; 3mg I2 and 7mg H2 are dissolved in the chlorobenzene, are made into the solution of 10 mg/ml, it is upper as luminescent layer to be spin-coated on PEDOT with 1500 rev/mins speed; Under the condition of vacuum, the DPSF that evaporation 50nm is thick on luminescent layer is as electron transfer layer, subsequently successively evaporation LiF and Al electrode.
The experiment structure shows: the bright voltage that opens of El element is 3.6V, and maximum luminous efficiency is 19.0cd/A, and maximum power efficiency is 16.0lm/W, high-high brightness 4700cd/m 2, chromaticity coordinates CIE value x=0.15, y=0.26.
Embodiment 10
Adopt I 2Assemble the electroluminescent device of non-doping, the structure of device is: ITO/PEDOT(40nm)/and I 2(40nm)/DPSF(50nm)/LiF(1nm)/Al(100nm).The packaging technology of device is as follows:
After conducting polymer polythiofuran derivative (PEDOT) is spin-coated on the ito glass surface of cleaning in advance with 3000 rev/mins speed, at 120 ℃ of lower baking 30min, forms the thick hole of 50nm and inject two-layer electrode, and improve the planarization on ito glass surface; With 10mg I 2Be dissolved in the chlorobenzene, be made into the solution of 10 mg/ml, it is upper as luminescent layer to be spin-coated on PEDOT with 1500 rev/mins speed; Under the condition of vacuum, the DPSF that evaporation 50nm is thick on luminescent layer is as electron transfer layer, subsequently successively evaporation LiF and Al electrode.
Fig. 2 is the graphic representation of brightness-voltage of the organic electroluminescence device of embodiment 10 and Comparative Examples preparation, and the ■ curve is the brightness-voltage curve of Comparative Examples device among the figure, and zero curve is the brightness-voltage curve of embodiment device; Fig. 3 is the graphic representation of luminous efficiency-brightness of the organic electroluminescence device of embodiment 10 and Comparative Examples preparation, and the ■ curve is the luminous efficiency-brightness curve of Comparative Examples device among the figure, and zero curve is the luminous efficiency-brightness curve of embodiment device; Fig. 4 is the graphic representation of power efficiency-brightness of the organic electroluminescence device of embodiment 10 and Comparative Examples preparation, and the ■ curve is the power efficiency-brightness curve of Comparative Examples device among the figure, and zero curve is the power efficiency-brightness curve of embodiment device; Fig. 5 is the luminous intensity-wavelength curve figure of the organic electroluminescence device of embodiment 10 and Comparative Examples preparation, and the ■ curve is the luminous intensity-wavelength curve of Comparative Examples device among the figure, and zero curve is the luminous intensity-wavelength curve of embodiment device.
The experiment structure shows: the bright voltage that opens of El element is 3.7V, and maximum luminous efficiency is 30.5cd/A, and maximum power efficiency is 29.0lm/W, high-high brightness 6800cd/m 2, chromaticity coordinates CIE value x=0.16, y=0.29.
Embodiment 11
Figure BDA00002633801300281
Adopt I 2Done main body, assembled green electrophosphorescence device, the structure of device is: ITO/PEDOT:PSS(40nm)/and I 2: G1 (30%) is (40nm)/DPSF(50nm)/LiF(1nm)/Al(100nm).The packaging technology of device is as follows:
After conducting polymer polythiofuran derivative (PEDOT) is spin-coated on the ito glass surface of cleaning in advance with 3000 rev/mins speed, at 120 ℃ of lower baking 30min, forms the thick hole of 50nm and inject two-layer electrode, and improve the planarization on ito glass surface; I with 10 mg/ml 2: G1 (30%) wiring solution-forming, it is upper as luminescent layer to be spin-coated on PEDOT with 1500 rev/mins speed; Under the condition of vacuum, the DPSF that evaporation 50nm is thick on luminescent layer is as electron transfer layer, subsequently successively evaporation LiF and Al electrode.
Fig. 6 is the graphic representation of the current efficiency-power power-brightness of embodiment 11, and the A curve is the current efficiency-brightness curve of embodiment device among the figure, and the B curve is the power efficiency-brightness curve of embodiment device; Fig. 7 is the graphic representation of the current density-brightness-voltage of the organic electroluminescence device of embodiment 11 preparation, and the A curve is the current density voltage curve of embodiment device among the figure, and the B curve is the brightness-voltage curve of embodiment device; Fig. 8 is the normalized electroluminescent spectrum of embodiment 11 when driving voltage is 6V.
The experiment structure shows: the bright voltage that opens of El element is 2.9V, and maximum luminous efficiency is 52.8cd/A, and maximum power efficiency is 48.4lm/W, high-high brightness 44107cd/m 2, chromaticity coordinates CIE value x=0.39, y=0.58.
Embodiment 12
Adopt I 2Done main body, assembling white phosphorus photoelectricity electroluminescence device, the structure of device is: ITO/PEDOT:PSS(40nm)/I 2: O1 (80:1) is (40nm)/DPSF(50nm)/LiF(1nm)/Al(100nm).The packaging technology of device is as follows:
After conducting polymer polythiofuran derivative (PEDOT) is spin-coated on the ito glass surface of cleaning in advance with 3000 rev/mins speed, at 120 ℃ of lower baking 30min, forms the thick hole of 50nm and inject two-layer electrode, and improve the planarization on ito glass surface; I with 10 mg/ml 2: O1 (80:1) wiring solution-forming, it is upper as luminescent layer to be spin-coated on PEDOT with 1500 rev/mins speed; Under the condition of vacuum, the DPSF that evaporation 50nm is thick on luminescent layer is as electron transfer layer, subsequently successively evaporation LiF and Al electrode.
Fig. 9 is the graphic representation of the current efficiency-power power-brightness of embodiment 12, and the A curve is the current efficiency-brightness curve of embodiment device among the figure, and the B curve is the power efficiency-brightness curve of embodiment device; Figure 10 is the graphic representation of the current density-brightness-voltage of the organic electroluminescence device of embodiment 12 preparation, and the A curve is the current density voltage curve of embodiment device among the figure, and the B curve is the brightness-voltage curve of embodiment device; Figure 11 is the normalized electroluminescent spectrum of embodiment 12 when driving voltage is 6.5V.
The experiment structure shows: the bright voltage that opens of El element is 3.1V, and maximum luminous efficiency is 35.9cd/A, and maximum power efficiency is 35.2lm/W, high-high brightness 10524cd/m 2, chromaticity coordinates CIE value x=0.35, y=0.39.
Comparative Examples
The electroluminescent device that adopts the FIrpic assembling to mix, the structure of device is: ITO/PEDOT(40nm)/H2:10wt%FIrpic(40nm)/DPSF(50nm)/LiF(1nm)/Al(100nm).The packaging technology of device is as follows:
After conducting polymer polythiofuran derivative (PEDOT) is spin-coated on the ito glass surface of cleaning in advance with 3000 rev/mins speed, at 120 ℃ of lower baking 30min, forms the thick hole of 50nm and inject two-layer electrode, and improve the planarization on ito glass surface; 1mg FIrpic and 9mg H2 are dissolved in the chlorobenzene, are made into the solution of 10 mg/ml, it is upper as luminescent layer to be spin-coated on PEDOT with 1500 rev/mins speed; Under the condition of vacuum, the DPSF that evaporation 50nm is thick on luminescent layer is as electron transfer layer, subsequently successively evaporation LiF and Al electrode.
The experiment structure shows: the bright voltage that opens of El element is 5.2V, and maximum luminous efficiency is 21.6cd/A, and maximum power efficiency is 10.0lm/W, high-high brightness 6700cd/m 2, chromaticity coordinates CIE value x=0.15, y=0.31.Table 1 is the performance data table of the organic electroluminescence device of embodiment and Comparative Examples preparation.
The performance data table of the organic electroluminescence device of table 1 embodiment and Comparative Examples preparation
Figure BDA00002633801300301
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be apparent concerning those skilled in the art, and General Principle as defined herein can in the situation that does not break away from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.

Claims (9)

1. dendroid blue light metal complexes shown in formula I,
Figure FDA00002633801200011
Wherein, M is Ir or Pt;
Q is independently selected from 0 or 1;
When M is Ir, p+q=3, when M is Pt, p+q=2;
Q 1And Q 2Independently be selected from N or CH, and Q 1During for CH, Q 1On hydrogen can be further by R 4Replace;
N is the algebraically of branch unit, is selected from 1,2,3,4 or 5;
R 1And R 2Be independently selected from alkyl, alkoxyl group or the alkylthio of hydrogen, fluorine, cyano group, C1 ~ C40, aryl, aryloxy or the arylthio of C6 ~ C60; Work as R 1And R 2When independently being selected from the alkyl, alkoxyl group of C1 ~ C40 or alkylthio, the hydrogen on the group can be further by one or more R 4Replace; Work as R 1And R 2When independently being selected from the aryl, aryloxy of C6 ~ C60 or arylthio, the hydrogen on the group can be further by one or more R 4Replace;
R 3Be independently selected from the alkyl of hydrogen or C1 ~ C40, work as R 3When independently being selected from the alkyl of C1 ~ C40, one or more hydrogen atoms can be by fluorine, CN or NO 2Substitute, or one or more non-adjacent CH 2Group can be substituted by O or S;
L is linking group, is formula V, formula (VI), and one or more in formula (VII) and formula (VIII) structure:
Figure FDA00002633801200021
Wherein, a, b, c, d, e independently are selected from the integer between 1 ~ 10;
Formula V, formula (VI), the hydrogen in formula (VII) and the formula (VIII) can be by R 4Replace;
R 4Be the alkyl of fluorine, cyano group, trifluoromethyl, pentafluoroethyl group, C1 ~ C6 or the alkoxyl group of C1 ~ C6;
X is for having the double dentate anion ligand of 1 ~ 30 carbon atom.
2. dendroid blue light metal complexes according to claim 1 is characterized in that described R 3The structure that consists of with described branch unit is a kind of in the following structure:
Figure FDA00002633801200022
R 3Definition and formula I in R 3Definition identical.
3. dendroid blue light metal complexes according to claim 1, it is characterized in that the double-tooth chelate ligand of the single anion that described X is single anion part with diketone structure, have carboxyl or have the double-tooth chelate ligand of the single anion of phenolic hydroxyl group.
4. each described dendroid blue light metal complexes is characterized in that Q according to claim 1 ~ 3 1For CH and hydrogen can be further by R 4Replace R 1And R 2Be independently selected from fluorine, trifluoromethyl, pentafluoroethyl group, cyano group.
5. each described dendroid blue light metal complexes is characterized in that Q according to claim 1 ~ 3 1Be N, R 1And R 2Be independently selected from the alkyl of fluorine, trifluoromethyl, pentafluoroethyl group, cyano group, C1 ~ C4, the alkoxyl group, 2 of C1 ~ C4,6-3,5-dimethylphenyl or phenoxy group.
6. each described dendroid blue light metal complexes application in organic electronic devices of claim 1 ~ 5.
7. organic light emitting diode device comprises: negative electrode, anode and at least one deck it is characterized in that as the organic layer of luminescent layer, contain at least a such as each described dendroid blue light metal complexes of claim 1 ~ 5 in the described luminescent layer.
8. Organic Light Emitting Diode according to claim 7 is characterized in that, each described dendroid blue light metal complexes of claim 1 ~ 5 is as the blue light emitting dyestuff in the Organic Light Emitting Diode.
9. Organic Light Emitting Diode according to claim 7 is characterized in that, each described dendroid blue light metal complexes of claim 1 ~ 5 is as the material of main part of phosphorescent coloring.
CN201210562940.0A 2012-12-21 2012-12-21 Dendritic blue light metal complex and application thereof and organic light emitting diode device Active CN102993180B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210562940.0A CN102993180B (en) 2012-12-21 2012-12-21 Dendritic blue light metal complex and application thereof and organic light emitting diode device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210562940.0A CN102993180B (en) 2012-12-21 2012-12-21 Dendritic blue light metal complex and application thereof and organic light emitting diode device

Publications (2)

Publication Number Publication Date
CN102993180A true CN102993180A (en) 2013-03-27
CN102993180B CN102993180B (en) 2016-03-30

Family

ID=47922351

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210562940.0A Active CN102993180B (en) 2012-12-21 2012-12-21 Dendritic blue light metal complex and application thereof and organic light emitting diode device

Country Status (1)

Country Link
CN (1) CN102993180B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105732722A (en) * 2016-03-10 2016-07-06 盐城工学院 Organic electrophosphorescence compound and electroluminescent device
CN109467983A (en) * 2018-12-14 2019-03-15 中国科学院长春应用化学研究所 A kind of small organic molecule luminescent material ink and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1772757A (en) * 2005-09-16 2006-05-17 中国科学院长春应用化学研究所 Dendritic iridium complex and organic electroluminescent device therewith
JP2007184348A (en) * 2006-01-05 2007-07-19 Konica Minolta Holdings Inc Organic electroluminescence element, display device, and lighting device
CN101108964A (en) * 2007-08-21 2008-01-23 中国科学院长春应用化学研究所 Arborization glowing iridium complex and organic EL device of the compound
JP2008174499A (en) * 2007-01-19 2008-07-31 Sumitomo Chemical Co Ltd Dendrimer complex compound, and method for producing another dendrimer complex compound utilizing the same
WO2011059787A2 (en) * 2009-10-29 2011-05-19 E. I. Du Pont De Nemours And Company Organic light-emitting diode luminaires

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1772757A (en) * 2005-09-16 2006-05-17 中国科学院长春应用化学研究所 Dendritic iridium complex and organic electroluminescent device therewith
JP2007184348A (en) * 2006-01-05 2007-07-19 Konica Minolta Holdings Inc Organic electroluminescence element, display device, and lighting device
JP2008174499A (en) * 2007-01-19 2008-07-31 Sumitomo Chemical Co Ltd Dendrimer complex compound, and method for producing another dendrimer complex compound utilizing the same
CN101108964A (en) * 2007-08-21 2008-01-23 中国科学院长春应用化学研究所 Arborization glowing iridium complex and organic EL device of the compound
WO2011059787A2 (en) * 2009-10-29 2011-05-19 E. I. Du Pont De Nemours And Company Organic light-emitting diode luminaires

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105732722A (en) * 2016-03-10 2016-07-06 盐城工学院 Organic electrophosphorescence compound and electroluminescent device
CN105732722B (en) * 2016-03-10 2019-05-17 盐城工学院 A kind of organic electrophosphorescenpolymer compound and a kind of electroluminescent device
CN109467983A (en) * 2018-12-14 2019-03-15 中国科学院长春应用化学研究所 A kind of small organic molecule luminescent material ink and preparation method thereof

Also Published As

Publication number Publication date
CN102993180B (en) 2016-03-30

Similar Documents

Publication Publication Date Title
CN103732602B (en) Metal complexes
TWI724003B (en) Metal complex and organic light-emitting device
CN103619860B (en) Metal complex
KR102615336B1 (en) Organic light-emitting materials based on platinum tetradentate ONCN complex, preparation method, and application thereof in organic light-emitting diodes
CN101759685B (en) Organic electroluminescent iridium coordination compound and preparation method and application thereof
CN105254562A (en) Organic small molecule luminescent material and organic electroluminescent device prepared from same
CN101910095A (en) Organic material containing oligophenylene skeleton and light-emitting device using the same
Cho et al. Tunable emission of polymer light emitting diodes bearing green-emitting Ir (III) complexes: The structural role of 9-((6-(4-fluorophenyl) pyridin-3-yl) methyl)-9H-carbazole ligands
CN101108964B (en) Arborization glowing iridium complex and organic EL device of the compound
He et al. Synthesis and optoelectronic properties of novel fluorene-bridged dinuclear cyclometalated iridium (III) complex with A–D–A framework in the single-emissive-layer WOLEDs
CN107033190A (en) A kind of phosphorescent iridium complex of alkenyl containing dish and preparation method thereof and electroluminescent device
Hwang et al. Synthesis and characterization of phenylpyridine derivative containing an imide functional group on an iridium (III) complex for solution-processable orange-phosphorescent organic light-emitting diodes
CN110407838A (en) Electroluminescent organic material and device
CN109790183A (en) Metal organic complex and its application, mixture, organic electronic device
CN102851024B (en) Organic electroluminescent material based on bis(2-diphenylphosphinophenyl)ether serving as ligand
CN102993180B (en) Dendritic blue light metal complex and application thereof and organic light emitting diode device
CN104370968A (en) Isoquinoline metal complex, and preparation method and application thereof
Liang et al. Novel dinuclear cyclometalated Platinum (II) complex as orange phosphorescent emitters for single-emitting-layer white polymer light-emitting diodes
CN102516310A (en) Cyclometalated iridium complex organic electrophosphorescent material, its preparation method and application
CN101580521B (en) Dendritic organic metal composition and electroluminescent device using same
CN103172679A (en) Iridium-containing organic electroluminescence blue light phosphorescence material, preparation method and organic electroluminescent device
CN113999266A (en) Binuclear metal platinum complex and organic electroluminescent device
CN110862350A (en) Pterene pyridazine tetradentate platinum complex phosphorescent material and preparation method and application thereof
CN104177446A (en) Organic electroluminescent material, and preparation method and application thereof
CN104177409A (en) Organic electroluminescence material and preparation method and application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant