CN101074237A - Phosphorescent multinuclear copper complex and organic electroluminescent device using the same - Google Patents
Phosphorescent multinuclear copper complex and organic electroluminescent device using the same Download PDFInfo
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- CN101074237A CN101074237A CNA2007101041441A CN200710104144A CN101074237A CN 101074237 A CN101074237 A CN 101074237A CN A2007101041441 A CNA2007101041441 A CN A2007101041441A CN 200710104144 A CN200710104144 A CN 200710104144A CN 101074237 A CN101074237 A CN 101074237A
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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Abstract
Provided are a high-efficiency phosphorescent multinuclear copper complex and an organic electroluminescent device using the complex. The multinuclear copper complex can be used to form an organic layer of an organic electroluminescent device, and the organic electroluminescent device using the complex can emit light in the yellow to red wavelength region of 560 nm to 630 nm as a high-efficiency photoluminescent material, and provides a high brightness and a low turn-on voltage.
Description
Technical field
The present invention relates to a kind of phosphorescent multinuclear copper complex and use its organic electroluminescent (EL) device, more particularly, relate to a kind of at yellow luminous phosphorescent multinuclear copper complex and comprise that this multinuclear copper complex forms the organic electroluminescence device of material as organic layer to the 560-630nm of red wavelength zone.
Background technology
Organic electroluminescent (EL) device be to use when when organic layer applies electric current because compound in fluorescence or phosphorescence organic compound thin layer (below, organic layer) of electronics and hole and the active display device of the luminescence phenomenon that causes.Organic electroluminescent (EL) device is in light weight, comprises better simply and less parts, has the structure that can make by simple process, produces high quality graphic and has wide visual angle.Organic electroluminescence device also can produce the active images of high color purity and have low power consumption and low driving voltage.Therefore, organic electroluminescence device has the electrical characteristic that are applicable to mobile electronic device.
In general, the structure of organic electroluminescence device comprises the anode of sequence stack on base material, hole transmission layer, luminescent layer, electron transfer layer, and negative electrode.Hole transmission layer, luminescent layer and electron transfer layer are the organic layers that is formed by organic compound.Principle of work with organic electroluminescence device of structure as mentioned above is as follows.When between anode and negative electrode, applying voltage, shift to luminescent layer by hole transmission layer by the anode injected holes.Electronics injects luminescent layer by electron transfer layer by negative electrode.Owing to compound the produce exciton of current carrier in luminescent layer.Exciton experience radiative decay sends the light of wavelength corresponding to the material band gap.
The material that is used to form the luminescent layer of organic electroluminescence device is divided into fluorescent material that uses the singlet state exciton and the phosphor material that uses triplet exciton according to emission mechanism.Luminescent layer is directly formed by fluorescent material or phosphor material or mixes suitable material of main part and form.As the result of electron excitation, singlet state exciton and triplet exciton generate in main body.At this, it is 1: 3 people such as (, Phys.Rev.B, 1999,60,14422) Baldo that statistics between singlet state exciton and the triplet exciton generates ratio.
In the organic electroluminescence device that uses fluorescent material as the material that is used to form luminescent layer, can not use the triplet exciton that in main body, generates.But, in the organic electroluminescence device that uses phosphor material as the material that is used to form luminescent layer, can use singlet state exciton and triplet exciton, therefore, can obtain 100% internal quantum efficiency (people such as Baldo, Nature, Vol.395,151-154,1998).Therefore, the use of phosphor material causes than luminous efficiency high when using fluorescent material.
As heavy metal such as Ir, Pt, Rh, or Pd is when being included in the organic molecule, owing to heavy atoms effect spins-track coupling and therefore, singlet state exciton and triplet exciton are mixed, even at room temperature also make it possible to transition and therefore effective phosphorescence thus.
As the high efficient luminous material that shows phosphorescence, reported to use to comprise transition metal such as iridium (Ir), the various materials of the transistion metal compound of platinum (Pt) etc.But for efficient, full-color display spare, still need be at yellow luminous phosphor material to the 560-630nm of red wavelength zone.
Pyrazoles salt (pyrazolate) part is important in coinage alloy (coin metal) chemistry.Beyond pyrazoles salt part passes through-and bidentate form and metal ion such as Cu (I), Ag (I), Au coordinate such as (I) and form polynuclear coordination compound.Coinage alloy pyrazoles salt can form tripolymer according to the substituting group form in reaction conditions and the pyrazoles salt portion-form, the tetramer, six aggressiveness and until polymkeric substance.Pyrazoles salt part is by playing the performance that the effect that helps electronics injected electrons hop improves organic EL device.
In these coinage alloy pyrazoles salt, have the multinuclear coinage alloy of fluoridizing pyrazoles salt part and have the very interesting characteristics of luminescence.Fluoridizing by auxiliary volatilization promotes film to form the decline that improves thermostability and oxidative stability and cause launching concentration quenching.
Mohammad (Mohammad A.Omary, Inorg Chem., 2003,42,8612) discloses to have and has been engaged to 2,4 of copper atom, the metal pyrazoles salt complex of 6-cholidine.This title complex sends light blue coloured light.
In addition, still continuously need metal fluoride pyrazoles salt complex compound, it is included in various parts that are engaged in the metal fluoride pyrazoles salt complex on the atoms metal and the characteristics of luminescence that has excellence at non-blue wavelength region.
Summary of the invention
The invention provides a kind of can be effectively at yellow luminous multinuclear copper complex to the 560-630nm of red wavelength zone.
The present invention also provides a kind of organic electroluminescent (EL) device that uses this multinuclear copper complex.
The multinuclear copper complex of formula 1 expression is provided according to an aspect of the present invention.
[formula 1]
Wherein A and B respectively do for oneself and comprise heteroatoms X and have the C of being selected from
5-C
20Group of naphthene base, C
6-C
20Aromatic yl group, C
1-C
20Heteroaryl groups, silyl-group, at least one substituent C of boryl group and hole transport part
2-C
20Heteroaromatic rings; With
The X of A and the X of B are N independently, P, S, or O.
The present invention also provides the multinuclear copper complex of formula 2 or formula 3 expressions.
[formula 2]
[formula 3]
Wherein A and B be identical or different and the replacement that comprises heteroatoms X of respectively doing for oneself or unsubstituted heteroaromatic rings or substituting group replacement or unsubstituted aliphatic series or aromatic group and A and B that is attached to X can be and be selected from C
5-C
20Group of naphthene base, C
6-C
20Aromatic yl group, C
1-C
20Heteroaryl groups, silyl-group, boryl group and hole transport part at least a;
The X of A and the X of B are N independently, P, S, or O; With
Y is key or is selected from replacement or unsubstituted C
1-C
20Alkylidene group, C replacement or unsubstituted
6-C
20Arylene group, C replacement or unsubstituted
5-C
20The cycloalkylidene group, C replacement or unsubstituted
1-C
20The heteroarylidene group, the group of silyl-group and boryl group.
In the formula 1
Can represent by one of following group independently separately.
[formula 4]
[formula 5]
[formula 6]
[formula 7]
[formula 8]
[formula 9]
[formula 10]
[formula 11]
[formula 12]
[formula 13]
[formula 14]
In with following formula 4 to 14, R
11, R
12, R
13, R
14, R
15, and R
16Be selected from independently of one another hydrogen, halogen atom ,-OR ,-N (R)
2,-P (R)
2,-POR ,-PO
2R ,-PO
3R ,-SR ,-Si (R)
3,-B (R)
2,-B (OR)
2,-C (O) R ,-C (O) OR ,-C (O) N (R) ,-CN ,-NO
2,-SO
2,-SOR ,-SO
2R ,-SO
3R, C
1-C
20Alkyl group and C
6-C
20Aromatic yl group; With
R is selected from hydrogen, halogen atom, replacement or unsubstituted C
1-C
20C alkyl group, replacement or unsubstituted
1-C
10C alkoxy base, replacement or unsubstituted
2-C
20C kiki alkenyl group, replacement or unsubstituted
2-C
20C alkynyl group, replacement or unsubstituted
1-C
20Assorted alkyl, replacement or unsubstituted C
6-C
40C aromatic yl group, replacement or unsubstituted
7-C
40C aromatic alkyl group, replacement or unsubstituted
7-C
40C kiki fang alkyl group, replacement or unsubstituted
2-C
40Heteroaryl groups and that replace or unsubstituted C
3-C
40The heteroaralkyl group.
The multinuclear copper complex of formula 1 expression can be one of compound of formula 15 and 16 expressions.
[formula 15]
[formula 16]
In with following formula 2 or formula 3,
It can be one of group of following formula 17 to 19 expressions.
[formula 17]
[formula 18]
[formula 19]
In with following formula 17 to 19, R
11, R
12, R
13, R
14, R
15, and R
16Be selected from independently of one another hydrogen, halogen atom ,-OR ,-N (R)
2,-P (R)
2,-POR ,-PO
2R ,-PO
3R ,-SR ,-Si (R)
3,-B (R)
2,-B (OR)
2,-C (O) R ,-C (O) OR ,-C (O) N (R) ,-CN ,-NO
2,-SO
2,-SOR ,-SO
2R ,-SO
3R, C
1-C
20Alkyl group and C
6-C
20Aromatic yl group; With
R is selected from hydrogen, halogen atom, replacement or unsubstituted C
1-C
20C alkyl group, replacement or unsubstituted
1-C
10C alkoxy base, replacement or unsubstituted
2-C
20C kiki alkenyl group, replacement or unsubstituted
2-C
20C alkynyl group, replacement or unsubstituted
1-C
20Assorted alkyl, replacement or unsubstituted C
6-C
40C aromatic yl group, replacement or unsubstituted
7-C
40C aromatic alkyl group, replacement or unsubstituted
7-C
40C kiki fang alkyl group, replacement or unsubstituted
2-C
40Heteroaryl groups and that replace or unsubstituted C
3-C
40The heteroaralkyl group.
The multinuclear copper complex of formula 2 expressions can be one of compound of formula 20 to 22 expressions.
[formula 20]
[formula 21]
[formula 22]
The multinuclear copper complex of formula 3 expressions can be one of compound of formula 23 to 25 expressions.
[formula 23]
[formula 24]
[formula 25]
According to a further aspect in the invention, be provided at the organic EL device that comprises organic layer between the pair of electrodes, described organic layer comprises a kind of in the above-mentioned multinuclear copper complex.
Description of drawings
Distincter and the better understanding that becomes of the understanding that the present invention is more complete, many above and other feature and advantage of the present invention following detailed description by the reference accompanying drawing, identical in the accompanying drawings Reference numeral is represented same or analogous assembly, wherein:
Figure 1A to 1F schematically illustrates the figure of the laminate structure of organic electroluminescent (EL) device according to embodiments of the present invention;
Fig. 2 is the figure of explanation according to the organic EL device of embodiment of the present invention;
Fig. 3 is the NMR spectrum of synthetic phosphorescent multinuclear copper complex (a) and isoquinoline 99.9 phenyl triphenylamine (b) in embodiment 1;
Fig. 4 is the thermogravimetric analysis result's of the phosphorescent multinuclear copper complex that obtains in embodiment 1 figure; With
Fig. 5 is the absorption spectrum of the phosphorescent multinuclear copper complex that obtains in embodiment 1, and photoluminescence (PL) spectrum and PL excite (PLE) spectrum;
Fig. 6 is to use the electroluminescent figure of the organic EL device of the phosphorescent multinuclear copper complex that obtains in embodiment 1;
Fig. 7 is the thermogravimetric analysis result's of the phosphorescent multinuclear copper complex that obtains in embodiment 3 figure;
Fig. 8 is the absorption spectrum and the PL spectrum of the phosphorescent multinuclear copper complex that obtains in embodiment 3;
Fig. 9 is the NMR spectrum of the phosphorescent multinuclear copper complex that obtains in embodiment 3;
Figure 10 is the mass spectrum of the phosphorescent multinuclear copper complex that obtains in embodiment 3;
Figure 11 is to use the figure of electric brightness (electroluminance) of the organic EL device of the phosphorescent multinuclear copper complex that obtains in embodiment 3; With
Figure 12 is the ORTEP figure of the phosphorescent multinuclear copper complex of acquisition in embodiment 3.
Embodiment
Below will describe the present invention in detail.
The multinuclear copper complex that the formula 1-3 of the invention provides represents.Because the electron transport ability of the excellence of pyrazoles utilizes the performance of the device of the copper complex that comprises metal pyrazoles salt part to be improved.In addition, owing to the heteroaromatic rings that is coordinated on the copper atom, charge transport ability excellence.
[formula 1]
In formula 1, A and B are independently of one another for comprising heteroatoms X and having the C of being selected from
5-C
20Group of naphthene base, C
6-C
20Aromatic yl group, C
1-C
20Heteroaryl groups, silyl-group, at least one substituent C of boryl group and hole transport part
2-C
6Heteroaromatic rings; With
The X of A and the X of B are N independently, P, S, or O.
Term " C
2-C
6Heteroaromatic rings " comprise have fused rings C
2-C
6Heteroaromatic rings and single aromatic ring.For example, C
2-C
6Heteroaromatic rings can comprise quinoline (that is the analogue that, has the pyridine of fused benzene rings) or indoles (that is the analogue that, has the pyrroles of fused benzene rings) and pyridine or pyrroles.
[formula 2]
[formula 3]
In formula 2 or 3, A and B are identical or different and the substituting group of respectively do for oneself replacement or the unsubstituted heteroaromatic rings that comprises heteroatoms X or the replacement that is attached to X or unsubstituted aliphatic series or aromatic group and A and B can be and is selected from C
5-C
20Group of naphthene base, C
6-C
20Aromatic yl group, C
1-C
20Heteroaryl groups, silyl-group, boryl group and hole transport part at least a;
The X of A and the X of B are N independently, P, S, or O; With
Y is key or is selected from replacement or unsubstituted C
1-C
20Alkylidene group, C replacement or unsubstituted
6-C
20Arylene group, C replacement or unsubstituted
5-C
20The cycloalkylidene group, C replacement or unsubstituted
1-C
20The heteroarylidene group, the group of silyl-group and boryl group.
In formula 3, copper atom be in the ligancy with distortion planar delta structure be 3+1 oxidation state.Each Cu (I) is coordinated to the electronegative N of an imidazoles, the neutral N and the X of second imidazoles.
In the formula 1
Can represent by one of following group independently separately.
[formula 4]
[formula 5]
[formula 6]
[formula 7]
[formula 8]
[formula 9]
[formula 10]
[formula 11]
[formula 12]
[formula 13]
[formula 14]
In with following formula 4 to 14, R
11, R
12, R
13, R
14, R
15, and R
16Be selected from independently of one another hydrogen, halogen atom ,-OR ,-N (R)
2,-P (R)
2,-POR ,-PO
2R ,-PO
3R ,-SR ,-Si (R)
3,-B (R)
2,-B (OR)
2,-C (O) R ,-C (O) OR ,-C (O) N (R) ,-CN ,-NO
2,-SO
2,-SOR ,-SO
2R ,-SO
3R, C
1-C
20Alkyl group and C
6-C
20Aromatic yl group; With
R is selected from hydrogen, halogen atom, replacement or unsubstituted C
1-C
20C alkyl group, replacement or unsubstituted
1-C
10C alkoxy base, replacement or unsubstituted
2-C
20C kiki alkenyl group, replacement or unsubstituted
2-C
20C alkynyl group, replacement or unsubstituted
1-C
20Assorted alkyl, replacement or unsubstituted C
6-C
40C aromatic yl group, replacement or unsubstituted
7-C
40C aromatic alkyl group, replacement or unsubstituted
7-C
40C kiki fang alkyl group, replacement or unsubstituted
2-C
40Heteroaryl groups and that replace or unsubstituted C
3-C
40The heteroaralkyl group.
The multinuclear copper complex of formula 1 expression can be one of compound of formula 15 and 16 expressions.
[formula 15]
[formula 15]
In with following formula 2,
It can be one of group of following formula 17 to 19 expressions.
[formula 17]
[formula 18]
[formula 19]
In with following formula 17 to 19, R
11, R
12, R
13, R
14, R
15, and R
16Be selected from independently of one another hydrogen, halogen atom ,-OR ,-N (R)
2,-P (R)
2,-POR ,-PO
2R ,-PO
3R ,-SR ,-Si (R)
3,-B (R)
2,-B (OR)
2,-C (O) R ,-C (O) OR ,-C (O) N (R) ,-CN ,-NO
2,-SO
2,-SOR ,-SO
2R ,-SO
3R, C
1-C
20Alkyl group and C
6-C
20Aromatic yl group; With
R is selected from hydrogen, halogen atom, replacement or unsubstituted C
1-C
20C alkyl group, replacement or unsubstituted
1-C
10C alkoxy base, replacement or unsubstituted
2-C
20C kiki alkenyl group, replacement or unsubstituted
2-C
20C alkynyl group, replacement or unsubstituted
1-C
20Assorted alkyl, replacement or unsubstituted C
6-C
40C aromatic yl group, replacement or unsubstituted
7-C
40C aromatic alkyl group, replacement or unsubstituted
7-C
40C kiki fang alkyl group, replacement or unsubstituted
2-C
40Heteroaryl groups and that replace or unsubstituted C
3-C
40The heteroaralkyl group.
The multinuclear copper complex of formula 2 expressions can be one of compound of formula 20 to 22 expressions.
[formula 20]
[formula 21]
[formula 22]
The multinuclear copper complex of formula 3 expressions can be one of compound of formula 23 to 25 expressions.
[formula 23]
[formula 24]
[formula 25]
In formula 1, the substituent example of A and B comprises: C
5-C
20Group of naphthene base such as cyclohexyl, cyclopentyl, ring octyl group etc.; C
6-C
20Aromatic yl group such as phenyl, 1,3-benzo dioxole, biphenyl, naphthalene, anthracene, Azulene etc.; C
1-C
20Heteroaryl groups such as thiophene, furans 2 (5H)-furanone, pyridine, tonka bean camphor, imidazoles, 2-phenylpyridine, 2-[4-morpholinodithio, 2-benzoxazol, 1-phenylpyrazole, 1-naphthyl pyrazoles, 5-(4-p-methoxy-phenyl) pyrazoles, 2,5-phenylbenzene-1,3,4- diazole, 2,3-cumarone 2-(4-xenyl)-6-phenyl benzoxazol etc.
The example of silyl-group comprises diarye silyl, trialkylsilkl etc.The example of boryl group comprises Dialkylborane base, diaryl boryl, boron difluoride alkyl, difluoro heteroaryl boryl etc.
The example of hole transport part comprises triazolyl, the azoles base of imidazolyl, benzimidazolyl-, triazolyl, the replacement of quinolyl, imidazolyl, the replacement of quinolyl, replacement, the azoles base, 1 of replacement, 1 of 10-diaza phenanthryl (phenantrolyl), replacement, the quinoxalinyl of 10-diaza phenanthryl, quinoxalinyl, replacement etc.
In with following formula 2 or 3, comprise C for the aliphatic series that is attached to X of A and B or the example of aromatic group
5-C
20Alkyl group, C
6-C
20Aromatic yl group, C
1-C
20Heteroaryl groups, C
3-C
20Group of naphthene base, etc.
According to the multinuclear copper complex of formula according to the present invention 1 expression can by with the compound of following formula 26 ([3,5-CF
3]
2Pz}-Cu}
3) (wherein Pz is a pyrazoles) and formula 27 and 28 expressions the reaction of heteroaromatic rings compounds and synthesize.
[formula 26]
[formula 27] [formula 28]
In formula 27 and 28, definition is identical in A, B and X and the following formula 1.
The method of the exemplary compounds of explanation preparation formula 1 in following reaction scheme 1.
＜reaction scheme 1 〉
Synthetic [3,5-(CF
3)
2Pz] Cu[parvoline base borine]
2
Reaction in the reaction scheme 1 can compound and the mol ratio between the parvoline base borine according to formula 26 25-40 ℃ under be carried out 24-48 hour in solvent such as benzene at 1: 3.
According to the multinuclear copper complexes of the formula 2 of embodiment of the present invention or 3 expressions can by with the compound of formula 26 ([3,5-CF
3]
2Pz}-Cu}
3) synthesize with the compound reaction of formula 29.
[formula 29]
In with following formula 29, A, B, X and Y are with identical with the definition in following formula 2 or 3.
Below in reaction scheme 2 method of explanation preparation formula 2 or 3 representative compounds.
＜reaction scheme 2 〉
Synthetic [3,5-(CF
3)
2Pz] Cu[4-(2-isoquinolyl) xenyl xylyl amine]
2
Reaction in the reaction scheme 2 can be in solvent such as benzene 25-40 ℃ under be carried out 24-48 hour according to the mol ratio between the compound of the compound of formula 26 and formula 29 at 2: 3.
Organic EL device according to the present invention comprises organic layer and the especially luminescent layer that one of copper complex by formula 1-3 forms.At this, the copper complex of formula 1-3 is to be used to form the very useful phosphorescent dopants of luminescent layer and to have the excellent characteristics of luminescence in yellow to the 560-630nm of red wavelength zone.
The copper complex of representing as formula 1-3 is during as phosphorescent dopants, and organic layer can further comprise and is selected from polymer body, the hybrid agent of polymkeric substance and low molecular weight material, at least a main body of lower molecular weight main body and non-luminescence polymer matrix.At this, can use any polymer body of the luminescent layer that is used to form organic EL device, lower molecular weight main body and non-luminescence polymer matrix.The example of polymer body comprises poly-(vinylcarbazole) (PVK), poly-fluorenes etc., but be not limited thereto.The example of lower molecular weight main body comprise CBP (4,4 '-N, N '-two carbazoles-biphenyl), 4,4 '-two [9-(3,6-biphenyl carbazyl)]-1-1,1 '-biphenyl, 9,10-two [(2 ', 7 '-tertiary butyl)-9 ', 9 " spiral shell two fluorenyl anthracenes, four fluorenes (terafluorene) etc., but be not limited thereto.The example of non-luminescence polymer matrix comprises polymethylmethacrylate, polystyrene etc., but is not limited thereto.
The amount of the copper complex of one of formula 1-3 expression can be that for example, the 1-30 weight part forms material based on 100 weight part luminescent layers.When the amount of copper complex is lower than 1 weight part, the quantity not sufficient of luminescent material, and therefore efficient and life-span decline.When the amount of copper complex surpasses 30 weight parts, triplet exciton cancellation and therefore, decrease in efficiency.In addition, when copper complex is introduced luminescent layer, can make in all sorts of ways as vacuum moulding machine, sputter, printing applies ink-jet etc.
In addition, the multinuclear copper complex represented of formula 1-3 can send white light when using with green luminescent material or blue emitting material.
Figure 1A to 1F schematically illustrates the figure of the laminate structure of organic EL device according to embodiments of the present invention.
With reference to Figure 1A, the luminescent layer 12 that comprises the copper complex of one of formula 1-3 forms on first electrode 10 and second electrode 14 forms on luminescent layer 12.
With reference to Figure 1B, the luminescent layer 12 that comprises the copper complex of one of formula 1-3 forms on first electrode 10, and hole blocking layer (HBL) 13 forms on HBL 13 at the formation and second electrode 14 on the luminescent layer 12.
Organic EL device among Fig. 1 C further is included in the hole injection layer (HIL) 11 that forms between first electrode 10 and the luminescent layer 12.
Organic EL device among Fig. 1 D have with Fig. 1 C in the identical laminate structure of organic EL device, except electron transfer layer (ETL) 15 replaces HBL 13 forming on the luminescent layer 12.
Organic EL device among Fig. 1 E have with Fig. 1 C in the identical laminate structure of organic EL device, except two-layer be HBL 13 and ETL 15, replace independent HBL 13, sequentially beyond forming on the luminescent layer 12 of the copper complex that comprises one of formula 1-3.If desired, the organic EL device of Fig. 1 E can further be included in the electron injecting layer between the ETL 15 and second electrode 14.
The organic EL device of Fig. 1 F has the structure identical with the organic EL device of Fig. 1 E, except hole transmission layer (HTL) 16 further forming between HIL 11 and the luminescent layer 12.HTL 16 prevents that impurity from entering luminescent layer 12 from HIL 11.
Having as mentioned above, the organic EL device of this laminate structure can use the general method manufacturing ad lib.
Organic layer can have organic layer thickness 30-100nm.When the thickness of organic layer during less than 30nm, its efficient and life-span descend.When the thickness of organic layer during greater than 100nm, operating voltage increases.
At this, organic layer is meant in organic EL device the layer that is formed by organic compound between the pair of electrodes.For example, organic layer can be luminescent layer, electron transfer layer, hole transmission layer etc.
In organic EL device, buffer layer can be inserted between each layer separately.The material that is used for buffer layer can be any material that is usually used in this field.The examples of material that is used for buffer layer generally includes copper phthalocyanine, Polythiophene, and polyaniline, polyacetylene, polypyrrole, polyphenylene vinylene and its derivative, but be not limited thereto.
The material that is used for hole transmission layer (HTL) can be any material that is usually used in this field, poly-triphenylamine for example, but be not limited thereto.
The material that is used for electron transfer layer (ETL) can be any material that is usually used in this field, polyoxadiazole for example, but be not limited thereto.
The material that is used for hole blocking layer (HBL) can be any material that is usually used in this field, LiF for example, BaF
2, or MgF
2, but be not limited thereto.
Organic EL device according to embodiment of the present invention need not to use particular device and method to make.For example, can make according to the method for using common luminescent material to make organic EL device according to the organic EL device of embodiment of the present invention.
Copper complex according to the formula 1-3 of embodiment of the present invention can send the light with the about 560-630nm of wavelength.Use the photodiode of this copper complex to can be used for full-color display, backlight, outdoor plate, optical communication, the light source of interior decoration etc.
Hereinafter with reference to the present invention of embodiment more detailed description.Following examples only are illustrative and are not used in and limit the scope of the invention.
Reference example 1: synthetic 3,5-(CF
3)
2Pz}}Cu
3}
With 0.40g (1.90mmole) Cu
2O and 1g (4.9mmole) 3 reacted 48-72 hour down in the 5-trifluoromethyl pyrazol adding 20-30mL benzene and at 60 ℃.Reaction product is cooled off and filtration under reduced pressure, and solvent is evaporated from reaction mixture.The gained white powder uses the mixture recrystallization of benzene and hexane.
1H NMR CDCl
3: ppm 6.97 (s, 1H, CH), 13.07-11.23 (wide, NH)
Embodiment 1: synthesis type 22 and 25 compound ([3,5-(CF
3)
2Pz] Cu[4-(2-isoquinolyl) xenyl xylyl amine]
2)
With 0.160g (0.2mmol) in reference example 1 synthetic 3,5-(CF
3)
2Pz}-Cu
3Reacted 48 hours in 30mL benzene with 0.111g (0.3mmol) isoquinolyl xenyl xylyl amine.After reaction terminating, use Celite to filter the reaction soln and in hexane precipitation to obtain the yellow-green colour solid chemical compound of formula 22 and 25.With the yellow-green colour pressed powder for several times and use the solution redeposition of benzene and hexane with hexane wash.By
1The structure of H NMR spectroscopic analysis and definite final product.The results are shown in Fig. 3.In Fig. 3, (a) be formula 22 and 25 multinuclear copper complex NMR spectrum and (b) be the NMR spectrum of isoquinolyl xenyl xylyl amine.Compare these two NMR spectrum, the pyrazoles peak appears in (a), shows the compound that has synthesized formula 22 and 25.
1H NMR CDCl
3：ppm 8.37(s，1H)，8.26(d，1H)，8.18(d，1H)，8.08(d，1H)，7.94(d，1H)，7.85(d，1H)，7.75(t，1H)，7.68(d，1H)，7.57(dd，4H)，7.2-7.04(m，10H)，7.03(s，2H)
19F NMR CDCl
3：ppm-61.23
The NMR data presentation form the possibility of above two kinds of structures.More than two kinds of structures are valence isomers.It is possible that these two kinds of structures exist in solution, because solvent helps the intersection (crossover) of the secondary valency 3 of the secondary valency 2 of the Cu (I) in first structure and the Cu (I) in second structure.
Embodiment 2: the compound of synthesis type 16 ([3,5-(CF
3)
2Pz] Cu[parvoline base borine]
2
With 0.160g (0.2mmol) in reference example 1 synthetic 3,5-(CF
3)
2Pz}-Cu
3Reacted 48 hours in 30mL benzene with 0.177g (1.2mmol) diethyl boryl pyridine.After reaction terminating, use Celite to filter the reaction soln and in hexane precipitation to obtain the colorless solid compounds of formula 16.With the colorless solid powder for several times and use the solution redeposition of benzene and hexane with hexane wash.By
1The structure of HNMR spectroscopic analysis and definite final product.
1H NMR CDCl
3：ppm 8.66(s，1H)，8.50(d，1H)，7.7(d，1H)，7.2(t，1H)，1.2(m，4H)，0.30(m，6H)
19F NMR CDCl
3：ppm-61.30
Embodiment 3: the compound of synthesis type 21 and formula 23 [3,5-(CF
3)
2Pz] Cu}
2[1,4-two (2-isoquinolyl) benzene]
With 0.160g (0.2mmol) in reference example 1 synthetic 3,5-(CF
3)
2Pz}-Cu
3Reacted 48 hours in 30mL benzene with 0.1g (0.3mmol) phenyl two isoquinoline 99.9.After reaction terminating, use Celite to filter the reaction soln and in hexane precipitation to obtain the yellow solid compound of formula 21 and 23.With the yellow solid powder for several times and use the solution redeposition of benzene and hexane with hexane wash.By
1The structure of HNMR spectroscopic analysis and definite final product.The results are shown in Fig. 9 and 10.In Fig. 9, except phenyl two isoquinoline 99.9 peaks, the pyrazoles peak has also appearred, show the compound that has synthesized formula 21 and 23.
1H NMR CDCl
3：ppm 8.61(d，1H)，8.20(d，1H)，8.03(d，1H)，7.94-7.83(m，2H)，7.68(t，1H)，7.58(s，2H)，6.6(s，1H)
19F NMR CDCl
3：ppm-61.00
The NMR data presentation forms the possibility of above two kinds of structures.But by under low pressure from its solution benzene slowly the monocrystalline that makes of evaporation or the crystalline structure of compound show and form second structure.The ORTEP figure of molecular structure is presented among Figure 12.
Embodiment 4: synthesis type 20 and 24 compound [3,5-(CF
3)
2Pz] Cu}
2[1,4-two (2-quinolyl) benzene]
With 0.160g (0.2mmol) in reference example 1 synthetic 3,5-(CF
3)
2Pz}-Cu
3Reacted 48 hours in 30mL benzene with 0.1g (0.3mmol) phenyl two quinoline.After reaction terminating, use Celite to filter the reaction soln and in hexane precipitation to obtain having the yellow solid compound of formula 20 and 24.With the yellow solid powder for several times and use the solution redeposition of benzene and hexane with hexane wash.By
1The structure of HNMR spectroscopic analysis and definite final product.
Embodiment 5: the compound of synthesis type 15 [3,5-(CF
3)
2Pz] Cu[4-(2-quinolyl) xenyl xylyl amine]
With 0.160g (0.2mmol) in reference example 1 synthetic 3,5-(CF
3)
2Pz}-Cu
3Reacted 48 hours in 30mL benzene with 0.222g (0.6mmol) isoquinolyl xenyl xylyl amine.After reaction terminating, use Celite to filter the reaction soln and in hexane precipitation to obtain the yellow-green colour solid chemical compound of formula 15.With the yellow-green colour pressed powder for several times and use the solution redeposition of benzene and hexane with hexane wash.By
1The structure of HNMR spectroscopic analysis and definite final product.
1H NMR CDCl
3：ppm 8.27(s，1H)，8.26(d，1H)，8.18(d，1H)，8.08(d，1H)，7.94(d，1H)，7.82(d，1H)，7.75(t，1H)，7.61(d，1H)，7.47(dd，4H)，7.0-6.89(m，10H)，6.79(s，1H)
19F NMR CDCl
3：ppm-61.15
The photoluminescence of the every kind of compound that in embodiment 1 to 4, obtains use every kind of compound dissolution in methylene dichloride 10
-4M solution and measuring.In addition, these compounds are spin-coated on the clean and tidy film photoluminescence with every kind of compound measuring form membrane respectively.
Photoluminescence of the compound that obtains in embodiment 1 to 4 (PL) and chromaticity coordinates (CIE) gather in table 1.The PL of the compound that obtains in embodiment 1 and 3 also provides in Fig. 5 and 8.
[table 1]
It is evident that from table 1, can produce doping agent and be suitable for use as in yellow to the luminous embedded photoluminescent material in red wavelength zone (560-630nm) with excellent photoluminescence property according to the multinuclear copper complex of embodiment of the present invention.
The multinuclear copper complex that obtains in embodiment 1 and 3 is carried out thermogravimetric analysis.The results are shown in Fig. 4 and 7.The multinuclear copper complex that obtains in embodiment 1 and 3 has the thermostability that decomposition temperature is the excellence of 210 ℃ and 265 ℃ respectively.
Make organic EL device
Embodiment 6
Resin and etching agent form and wash the ITO layer patternization by making with photoresist for transparency electrode base material washing that tin indium oxide (ITO) is applied and ITO electrode pattern.With PEDOT{ poly-(3, the 4-Ethylenedioxy Thiophene) } [CH 8000] be coated on the washed structure to the about 50nm of thickness and 120 ℃ down about 5 minutes of baking with the formation hole injection layer.
8% doping agent (embodiment 1) and main body (mHost5: PBD: TPD=12: 8: 3) be dissolved in that solution in the chloroform is spin-coated on the hole injection layer and 100 ℃ of bakings 1 hour down.Solvent is removed the luminescent layer that has thickness 50nm with formation fully from coating in vacuum oven.
Then, use vacuum deposition apparatus 4 * 10 TPBI
-6Holder or lower vacuum under pressure are deposited on the electron transfer layer that has thickness 45nm on the luminescent layer with formation.Then, LiF on the electron transfer layer speed under 0.1 /second vacuum moulding machine have the electron injecting layer of thickness 0.8nm with formation.
Subsequently, Al has the anode of thickness 150nm in speed 10 /second deposit with formation.At last, with the resulting structures sealing, obtain organic EL device like this.At this, seal process is undertaken by following: the BaO powder is put into metal tin, forms sealing agent at the edge of base material, and use the UV stiffening agent in glove box at dried this metal tin of nitrogen atmosphere lower seal to seal this structure.
Organic EL device has multilayered structure shown in Figure 2 and the light emission area is 6mm
2
Embodiment 7
Make organic EL device in the mode identical, except the compound of use formula 3 substitutes the compound of formula 1 with embodiment 6.
The electroluminescence characters of the organic EL device of in embodiment 5 and 6, making, chromaticity coordinates (CIE), luminance efficiency is connected voltage and brightness and is provided in table 2.
[table 2]
| ELλ max(nm) | CIE(x，y) | Luminance efficiency (Cd/A) | Connect voltage (V) | |
| Embodiment 6 | 600 | (0.53，0.43) | Under 11.0V 0.7 | 9 |
| Embodiment 7 | 600 | (0.52，0.45) | Under 5.0V 2.8 | 4.6 |
It is evident that from table 2, comprise the embodiment 6 of compound of the compound of embodiment 1 and embodiment 3 and 7 organic EL device respectively and to the 560-630nm of red wavelength zone, have high brightness in yellow, can under low voltage, work and have the high brightness efficient under high-voltage.
The variation of the luminance efficiency relative voltage of the variation of the electroluminescent intensity relative wavelength of the organic EL device of making in embodiment 6 and 7 and the organic EL device made in embodiment 6 and 7 provides in Fig. 6 and 11 respectively.When multinuclear copper complex according to the present invention is used as doping agent, on above-mentioned all characteristics, all be improved.
As mentioned above, can be luminous in the regional 560-630nm in yellow effectively according to multinuclear copper complex of the present invention to red wavelength.This multinuclear copper complex can be used for forming the organic layer of organic EL device and can be used as the high efficiency phosphorescent material luminous to the 560-630nm of red wavelength zone in yellow.This multinuclear copper complex can send white light when using with green luminescent material or blue emitting material.
Although specifically shown with reference to its exemplary and described the present invention, but those skilled in the art are to be understood that, do not deviating under the situation of the spirit and scope of the invention that limits by claims, can carry out various variations in form and details.
Claims (18)
1. the multinuclear copper complex of one of formula 1-3 expression:
[formula 1]
Wherein A and B are independently of one another for comprising heteroatoms X and having the C of being selected from
5-C
20Group of naphthene base, C
6-C
20Aromatic yl group, C
1-C
20Heteroaryl groups, silyl-group, at least one substituent C of boryl group and hole transport part
2-C
6Heteroaromatic rings; With
The X of A and the X of B are N independently, P, S, or O;
[formula 2]
[formula 3]
Wherein A and B are identical or different and the substituting group of respectively do for oneself replacement or the unsubstituted heteroaromatic rings that comprises heteroatoms X or the replacement that is attached to X or unsubstituted aliphatic series or aromatic group and A and B can be and is selected from C
5-C
20Group of naphthene base, C
6-C
20Aromatic yl group, C
1-C
20Heteroaryl groups, silyl-group, boryl group and hole transport part at least a;
The X of A and the X of B are N independently, P, S, or O; With
Y is key or is selected from replacement or unsubstituted C
1-C
20Alkylidene group, C replacement or unsubstituted
6-C
20Arylene group, C replacement or unsubstituted
5-C
20The cycloalkylidene group, C replacement or unsubstituted
1-C
20The heteroarylidene group, the group of silyl-group and boryl group.
2. an organic electroluminescence device is included in the organic layer between the pair of electrodes, and this organic layer comprises the multinuclear copper complex of claim 1.
3. the organic electroluminescence device of claim 2, wherein this organic layer is a luminescent layer.
4. the organic electroluminescence device of claim 3 wherein forms material based on 100 weight part luminescent layers, and the amount of this multinuclear copper complex is the 1-30 weight part.
5. the organic electroluminescence device of claim 2, wherein this organic layer further comprises at least a main body of the hybrid agent, lower molecular weight main body and the non-luminescence polymer matrix that are selected from polymer body, polymkeric substance and low molecular weight material.
6. the organic electroluminescence device of claim 2, wherein this organic layer further comprises one of green luminescent material and blue emitting material.
7. the multinuclear copper complex of formula 1 expression:
[formula 1]
Wherein A and B are independently of one another for comprising heteroatoms X and having the C of being selected from
5-C
20Group of naphthene base, C
6-C
20Aromatic yl group, C
1-C
20Heteroaryl groups, silyl-group, at least one substituent C of boryl group and hole transport part
2-C
6Heteroaromatic rings; With
The X of A and the X of B are N independently, P, S, or O.
8. the multinuclear copper complex of claim 7, in its Chinese style 1
[formula 4]
[formula 5]
[formula 6]
[formula 7]
[formula 8]
[formula 9]
[formula 10]
[formula 11]
[formula 12]
[formula 13]
[formula 14]
R wherein
11, R
12, R
13, R
14, R
15And R
16Be selected from independently of one another hydrogen, halogen atom ,-OR ,-N (R)
2,-P (R)
2,-POR ,-PO
2R ,-PO
3R ,-SR ,-Si (R)
3,-B (R)
2,-B (OR)
2,-C (O) R ,-C (O) OR ,-C (O) N (R) ,-CN ,-NO
2,-SO
2,-SOR ,-SO
2R ,-SO
3R, C
1-C
20Alkyl group and C
6-C
20Aromatic yl group; With
R is selected from hydrogen, halogen atom, replacement or unsubstituted C
1-C
20C alkyl group, replacement or unsubstituted
1-C
10C alkoxy base, replacement or unsubstituted
2-C
20C kiki alkenyl group, replacement or unsubstituted
2-C
20C alkynyl group, replacement or unsubstituted
1-C
20Assorted alkyl, replacement or unsubstituted C
6-C
40C aromatic yl group, replacement or unsubstituted
7-C
40C aromatic alkyl group, replacement or unsubstituted
7-C
40C kiki fang alkyl group, replacement or unsubstituted
2-C
40Heteroaryl groups and that replace or unsubstituted C
3-C
40The heteroaralkyl group.
9. the multinuclear copper complex of claim 7 is one of formula 15 and 16 compounds of representing
[formula 15]
[formula 16]
10. the multinuclear copper complex of claim 7, wherein said at least one substituting group is selected from cyclohexyl, cyclopentyl, ring octyl group, phenyl, 1,3-benzo dioxole, biphenyl, naphthalene, anthracene, Azulene, thiophene, furans 2 (5H)-furanone, pyridine, tonka bean camphor, imidazoles, 2-phenylpyridine, 2-[4-morpholinodithio, 2-benzoxazol, 1-phenylpyrazole, 1-naphthyl pyrazoles, 5-(4-p-methoxy-phenyl) pyrazoles, 2,5-phenylbenzene-1,3,4- diazole and 2,3-cumarone 2-(4-xenyl)-6-phenyl benzoxazol.
11. the multinuclear copper complex of claim 7, wherein silyl is diarye silyl or trialkylsilkl;
Boryl is Dialkylborane base, diaryl boryl, boron difluoride alkyl or difluoro heteroaryl boryl; With
Hole transport partly is selected from triazolyl, the azoles base of imidazolyl, benzimidazolyl-, triazolyl, the replacement of quinolyl, imidazolyl, the replacement of quinolyl, replacement, the azoles base, 1 of replacement, 1 of 10-diaza phenanthryl, replacement, 10-diaza phenanthryl, quinoxalinyl or the quinoxalinyl that replaces.
12. the multinuclear copper complex of formula 2 or 3 expressions:
[formula 2]
[formula 3]
Wherein A and B are identical or different and the substituting group of respectively do for oneself replacement or the unsubstituted heteroaromatic rings that comprises heteroatoms X or the replacement that is attached to X or unsubstituted aliphatic series or aromatic group and A and B can be and is selected from C
5-C
20Group of naphthene base, C
6-C
20Aromatic yl group, C
1-C
20Heteroaryl groups, silyl-group, boryl group and hole transport part at least a;
The X of A and the X of B are N independently, P, S, or O; With
Y is key or is selected from replacement or unsubstituted C
1-C
20Alkylidene group, C replacement or unsubstituted
6-C
20Arylene group, C replacement or unsubstituted
5-C
20The cycloalkylidene group, C replacement or unsubstituted
1-C
20The heteroarylidene group, the group of silyl-group and boryl group.
13. the multinuclear copper complex of claim 12, in its Chinese style 2 or 3
Be one of group by formula 17 to 19 expressions:
[formula 17]
[formula 18]
[formula 19]
R wherein
11, R
12, R
13, R
14, R
15And R
16Be selected from independently of one another hydrogen, halogen atom ,-OR ,-N (R)
2,-P (R)
2,-POR ,-PO
2R ,-PO
3R ,-SR ,-Si (R)
3,-B (R)
2,-B (OR)
2,-C (O) R ,-C (O) OR ,-C (O) N (R) ,-CN ,-NO
2,-SO
2,-SOR ,-SO
2R ,-SO
3R, C
1-C
20Alkyl group and C
6-C
20Aromatic yl group; With
R is selected from hydrogen, halogen atom, replacement or unsubstituted C
1-C
20C alkyl group, replacement or unsubstituted
1-C
10C alkoxy base, replacement or unsubstituted
2-C
20C kiki alkenyl group, replacement or unsubstituted
2-C
20C alkynyl group, replacement or unsubstituted
1-C
20Assorted alkyl, replacement or unsubstituted C
6-C
40C aromatic yl group, replacement or unsubstituted
7-C
40C aromatic alkyl group, replacement or unsubstituted
7-C
40C kiki fang alkyl group, replacement or unsubstituted
2-C
40Heteroaryl groups and that replace or unsubstituted C
3-C
40The heteroaralkyl group.
14. the multinuclear copper complex of claim 12, wherein silyl is diarye silyl or trialkylsilkl;
Boryl is Dialkylborane base, diaryl boryl, boron difluoride alkyl or difluoro heteroaryl boryl; With
Hole transport partly is selected from triazolyl, the azoles base of imidazolyl, benzimidazolyl-, triazolyl, the replacement of quinolyl, imidazolyl, the replacement of quinolyl, replacement, the azoles base, 1 of replacement, 1 of 10-diaza phenanthryl, replacement, 10-diaza phenanthryl, quinoxalinyl or the quinoxalinyl that replaces.
15. the multinuclear copper complex of claim 12 is one of compound of formula 20 to 24 expression:
[formula 20]
[formula 21]
[formula 22]
[formula 23]
[formula 24]
[formula 25]
16. the multinuclear copper complex of claim 12, wherein aliphatic series that is attached to X or the aromatic group for A and B is C independently
5-C
20Alkyl group, C
6-C
20Aromatic yl group, C
1-C
20Heteroaryl groups, or C
3-C
20Group of naphthene base.
17. the method for a synthetic multinuclear copper complex by one of formula 1-3 expression, this method comprises: with the compound of formula 26 ([3,5-CF
3]
2Pz}-Cu)
3) react with the heteroaromatic rings compound of formula 27 and 28 expressions or the compound of formula 29 expressions:
[formula 1]
Wherein A and B are independently of one another for comprising heteroatoms X and having the C of being selected from
5-C
20Group of naphthene base, C
6-C
20Aromatic yl group, C
1-C
20Heteroaryl groups, silyl-group, at least one substituent C of boryl group and hole transport part
2-C
6Heteroaromatic rings; With
The X of A and the X of B are N independently, P, S, or O;
[formula 2]
[formula 3]
Wherein A and B are identical or different and the substituting group of respectively do for oneself replacement or the unsubstituted heteroaromatic rings that comprises heteroatoms X or the replacement that is attached to X or unsubstituted aliphatic series or aromatic group and A and B can be and is selected from C
5-C
20Group of naphthene base, C
6-C
20Aromatic yl group, C
1-C
20Heteroaryl groups, silyl-group, boryl group and hole transport part at least a;
The X of A and the X of B are N independently, P, S, or O; With
Y is key or is selected from replacement or unsubstituted C
1-C
20Alkylidene group, C replacement or unsubstituted
6-C
20Arylene group, C replacement or unsubstituted
5-C
20The cycloalkylidene group, C replacement or unsubstituted
1-C
20The heteroarylidene group, the group of silyl-group and boryl group;
[formula 26]
[formula 27] [formula 28]
Definition identical in the A in formula 27 and 28, B and X and the formula 1 wherein;
[formula 29]
Definition identical in the A in formula 29, B, X and Y and formula 2 or 3 wherein.
18. pass through the multinuclear copper complex of the method synthetic of claim 17 by one of formula 1-3 expression.
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| CN106831829A (en) * | 2017-02-15 | 2017-06-13 | 黑龙江大学 | A kind of double phosphine copper cluster electroluminescent materials of feature based on dibenzofurans group and preparation method and application |
| CN106831865A (en) * | 2017-02-15 | 2017-06-13 | 黑龙江大学 | A kind of double phosphine copper cluster electroluminescent materials of feature based on dibenzothiophenes group and preparation method and application |
| CN107074891A (en) * | 2014-10-06 | 2017-08-18 | 陶氏环球技术有限责任公司 | Copper (I) pyrazolate dimer for electroluminescent device |
| CN109705343A (en) * | 2018-12-12 | 2019-05-03 | 上海交通大学 | Azulenyl covalent triazine skeleton and its application |
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| KR100773524B1 (en) * | 2003-12-24 | 2007-11-07 | 삼성에스디아이 주식회사 | Binuclear organometallic complexes and organic electroluminescent display device using the same |
| KR101015882B1 (en) * | 2004-10-11 | 2011-02-23 | 삼성모바일디스플레이주식회사 | Cyclometalated transition metal complex and organic electroluminescence device using the same |
| KR101325062B1 (en) * | 2006-05-19 | 2013-11-05 | 삼성디스플레이 주식회사 | Luminescent heteronuclear copper(I)-iridium(III) complex and organic electroluminescence device using the same |
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| CN106831829A (en) * | 2017-02-15 | 2017-06-13 | 黑龙江大学 | A kind of double phosphine copper cluster electroluminescent materials of feature based on dibenzofurans group and preparation method and application |
| CN106831865A (en) * | 2017-02-15 | 2017-06-13 | 黑龙江大学 | A kind of double phosphine copper cluster electroluminescent materials of feature based on dibenzothiophenes group and preparation method and application |
| CN106831829B (en) * | 2017-02-15 | 2019-01-08 | 黑龙江大学 | A kind of double phosphine copper cluster electroluminescent materials of functionality based on dibenzofurans group and preparation method and application |
| CN106831865B (en) * | 2017-02-15 | 2019-01-08 | 黑龙江大学 | A kind of double phosphine copper cluster electroluminescent materials of functionality based on dibenzothiophenes group and preparation method and application |
| CN109705343A (en) * | 2018-12-12 | 2019-05-03 | 上海交通大学 | Azulenyl covalent triazine skeleton and its application |
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