CN101468973A - Organometallic compounds for electroluminescence and organic electroluminescent device using the same - Google Patents
Organometallic compounds for electroluminescence and organic electroluminescent device using the same Download PDFInfo
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- CN101468973A CN101468973A CNA200810178516XA CN200810178516A CN101468973A CN 101468973 A CN101468973 A CN 101468973A CN A200810178516X A CNA200810178516X A CN A200810178516XA CN 200810178516 A CN200810178516 A CN 200810178516A CN 101468973 A CN101468973 A CN 101468973A
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Abstract
The present invention relates to electroluminescent compounds represented by Chemical Formula (1) L1 L 1 M(Q) m and electroluminescent devices comprising the same as host material. The electroluminescent compound according to the invention, when used as host material of an OLED, noticeably lowers the operation voltage and enhance the power efficiency.
Description
Technical field
The present invention relates to comprise the electroluminescent compounds of metal complexes and contain the electroluminescent device of described electroluminescent compounds as substrate material, described electroluminescent compounds shows excellent electric conductivity and high efficiency light-emitting performance.
Background technology
The most important factor of decision luminous efficiency is the type of electroluminescent material in OLED.Although fluorescent material has been widely used as electroluminescent material so far, consider electroluminescent mechanism, the research and development phosphor material is luminous efficiency to be brought up in theory one of best approach of 4 times more than.
Up to now, iridium (III) title complex is the phosphor material of common general knowledge, comprises (acac) Ir (btp) that is respectively redness, green and blue phosphorescent material
2, Ir (ppy)
3And Firpic.In particular, recently in Japan, Europe and the U.S., a large amount of phosphor materials has obtained research.
As the substrate material of phosphorescent luminescent material, CBP the most generally knows so far, and it also is known that the hole blocking layer (for example BCP and BAlq) of paint on it had high efficiency OLEPs.Pioneer (Japan) etc. has reported and has used the BAlq derivative as the high efficiency OLEDs of having of matrix.
Although material of the prior art has superiority on luminescent properties, they have the thermostability of low second-order transition temperature and non-constant, so that they change in the high temperature gas phase deposition process in a vacuum easily.In organic electroluminescence device (OLED), definable specific power=(Π/voltage) * current efficiency.Therefore, specific power and voltage are inversely proportional to, and in order to obtain lower OLED energy waste, specific power should be higher.In fact, adopt the OLED of phosphorescence electroluminescent (EL) material to demonstrate obvious higher current efficiency (cd/A) than the OLED that adopts fluorescence EL material.Yet, under the situation of traditional material that adopts such as BAlq and CBP,, do not having remarkable advantages aspect the specific power (1m/w) because compare higher operating voltage with the OLED that adopts fluorescent material as the substrate material of phosphorescence EL material.
The present inventor has invented the EL compound of being represented by following structure, and described compound comprises the skeleton of mixed type coordination metal complexes, has than traditional organic substrate material or much better EL performance and the physicals of aluminum complex; Foregoing is submitted to and is korean patent application No.2006-7467.
Since the mid-90 in 19th century, as the EL material, blue light EL material for example, such traditional title complex is studied widely.Yet those materials only are applied as the EL material, and seldom use as the substrate material of phosphorescence EL material.
Simultaneously, the open No.2002-305083 of Japanese patent unexamined has measured the device efficiency of the compound that illustrates below, and wherein thiazole, benzothiazole and phenyl ring are not replaced by any substituting group except hydrogen.The compound that does not openly have different substituents.Be known that compd B provides at 100cd/m
2The operating voltage of the specific power of following 2.61m/w, the luminous efficiency of 5.3cd/A and 6.5V does not have other substituent any situation but be described on the part.
Summary of the invention
According to the present invention, researched and developed a kind of metal complexes material, to compare with traditional material, it shows excellent stability of material, better electric conductivity and high efficiency EL performance.Be included in and have a right heteroatoms of unpaired electron in the aromatic ring or in the side chain substituents, have strong trend with metal-complexing.This coordinate bond with highly stable chemical property is the general known performance of title complex.By means of a kind of like this performance, the present invention has researched and developed different ligands and prepared metal complexes, and they are then as substrate material.
The objective of the invention is to overcome the problems referred to above of conventional art, and the electroluminescent compounds with coordination metal complexes skeleton is provided, described compound is compared with traditional organic substrate material, demonstrates very excellent electroluminescent properties and physicals.Another object of the present invention provides electroluminescent device, and it comprises the described electroluminescent compounds for preparing as substrate material.
Therefore, the present invention relates to electroluminescent compounds of representing by chemical formula (1) and the electroluminescent device that comprises as the described compound of substrate material.
Chemical formula 1
L
1L
1M(Q)
m
Wherein, ligand L
1Have structure as follows:
M represents divalence or trivalent metal;
M is 0 when M is divalent metal, and m is 1 when M is trivalent metal;
Q representative (C6 to C60) aryloxy or three (C6 to C30) aryl silyl, the aryloxy of Q or diarye silyl can further be replaced by straight or branched (C1 to a C60) alkyl or (C1 to C60) aryl;
When X represented O, ring A was selected from down array structure:
When X represented S, ring A was selected from down array structure:
R
1To R
4Represent hydrogen, (C1 to C60) alkyl, halogen, cyano group, (C3 to C60) cycloalkyl, (C6 to C60) aryl, (C4 to C60) heteroaryl, single or two (C1 to C30) alkylamino, single or two (C6 to C30) virtue amino, three (C1 to C30) alkyl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl or three (C6 to C30) aryl silyl independently, maybe can pass through (C3 to C12) alkylene or (C3 to C12) thereby the adjacent substituting group formation fused rings of alkenylene connection;
R
11To R
17Represent hydrogen, (C1 to C60) alkyl, (C6 to C60) aryl, (C4 to C60) heteroaryl, three (C1 to C30) alkyl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl, three (C6 to C30) aryl silyl, single or two (C1 to C30) alkylamino, single or two (C6 to C30) virtue amino, cyano group or halogen independently, or R
13To R
16Can pass through (C3 to C12) alkylene or (C3 to C12) thereby the adjacent substituting group formation fused rings of alkenylene connection;
R
21To R
39Represent hydrogen, (C1 to C60) alkyl, (C6 to C60) aryl, (C4 to C60) heteroaryl, three (C1 to C30) alkyl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl, three (C6 to C30) aryl silyl, single or two (C1 to C30) alkylamino, single or two (C6 to C30) virtue amino, cyano group or halogen independently;
R
1To R
4Alkyl, aryl or heteroaryl, the fused rings that perhaps connects adjacent substituting group and form thus by (C3 to C12) alkylene or (C3 to C12) alkenylene, can further be replaced by one or more substituting groups, described substituting group is selected from (C1 to C60) alkyl, (C1 to the C60) alkyl that is replaced by halogen, (C6 to C60) aryl, three (C1 to C30) aryl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl, three (C6 to C30) aryl silyl, single or two (C1 to C30) alkylamino, single or two (C6 to C30) virtue is amino, cyano group and halogen;
R
11To R
16And R
21To R
39Alkyl, aryl or heteroaryl can further be replaced (C1 to C60) alkyl, halogen, (C6 to C60) aryl, single or two (C1 to C30) alkylamino, single or two (C6 to C30) virtue amino, three (C1 to C30) aryl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl, three (C6 to C30) aryl silyl and cyano group that described substituting group is selected from (C1 to C60) alkyl, is replaced by halogen by one or more substituting groups.
Ligand L
1Can be selected from following structure:
R wherein
1, R
2, R
3And R
4Have with the definition in the Chemical formula 1;
R
11To R
16(C1 to C60) alkyl, phenyl, naphthyl, xenyl, fluorenyl, three (C1 to C30) alkyl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl, three (C6 to C30) aryl silyl, two (C1 to C30) alkylamino, two (C6 to the C30) virtue of representing hydrogen, (C1 to C60) alkyl, halogen independently, being replaced by halogen is amino, thiophenyl or furyl;
R
17Representative (C1 to C60) alkyl, phenyl or naphthyl;
R
21And R
22(C1 to C60) alkyl, phenyl, naphthyl, xenyl, fluorenyl, three (C1 to C30) alkyl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl, three (C6 to C30) aryl silyl, two (C1 to C30) alkylamino, two (C6 to the C30) virtue of representing hydrogen, (C1 to C60) alkyl, halogen independently, being replaced by halogen is amino, thiophenyl or furyl;
R
23Representative (C1 to C60) alkyl, phenyl or naphthyl;
R
24To R
39(C1 to C60) alkyl, phenyl, naphthyl, xenyl, fluorenyl, three (C1 to C30) alkyl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl, three (C6 to C30) aryl silyl, two (C1 to C30) alkylamino, two (C6 to the C30) virtue of representing hydrogen, (C1 to C60) alkyl, halogen independently, being replaced by halogen is amino, thiophenyl or furyl;
R
40To R
43(C1 to C60) alkyl, phenyl, naphthyl, xenyl, fluorenyl, three (C1 to C30) alkyl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl, three (C6 to C30) aryl silyl, two (C1 to C30) alkylamino, the fragrant amino of two (C6 to C30) or the halogen representing hydrogen, (C1 to C60) alkyl independently, replaced by halogen; With
R
11To R
17, R
21To R
39And R
40To R
43Phenyl, naphthyl, xenyl, fluorenyl, thiophenyl or furyl can further be replaced by one or more substituting groups, described substituting group is selected from (C1 to C60) alkyl, halogen, phenyl, naphthyl, fluorenyl, three (C1 to C30) alkyl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl, three (C6 to C30) aryl silyl, two (C1 to C30) alkylamino or two (C6 to C30) virtue is amino.
Ligand L
1Preferably be selected from following structure:
Wherein, R
1To R
4Represent hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, chlorine, fluorine, phenyl, xenyl, naphthyl, fluorenyl, thiophenyl, trimethyl silyl, triphenyl silyl, t-butyldimethylsilyl, dimethylamino, diethylin or diphenylamino independently, get rid of wherein R
1, R
2, R
3And R
4All represent simultaneously the situation of hydrogen;
R
11And R
12Represent methylidene, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, trimethyl silyl, triphenyl silyl, phenyl, xenyl, naphthyl or fluorenyl independently;
R
13To R
16Represent methylidene, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, trimethyl silyl, triphenyl silyl, phenyl, xenyl, naphthyl or fluorenyl independently;
R
17Represent methylidene, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl or naphthyl;
R
21And R
22Represent hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, fluorine, trifluoromethyl, phenyl, naphthyl, xenyl, trimethyl silyl, triphenyl silyl, dimethylamino, diphenylamino, thiophenyl or furyl independently;
R
25And R
26Represent hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, fluorine, trifluoromethyl, phenyl, naphthyl, xenyl, trimethyl silyl, triphenyl silyl, dimethylamino, diphenylamino, thiophenyl or furyl independently; With
R
1, R
2, R
3, R
4, R
11, R
12, R
13, R
14, R
15, R
16, R
17, R
21, R
22, R
25And R
26Phenyl, xenyl, naphthyl, fluorenyl and thiophenyl can further be replaced by one or more substituting groups, described substituting group is selected from fluorine, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, TMS, tertiary butyl dimethylsilyl, phenyl, naphthyl, fluorenyl, dimethylamino, diethylin and diphenylamino.
In chemical formula (1), M is the divalent metal that is selected from Be, Zn, Mg, Cu and Ni, perhaps be selected from the trivalent metal of Al, Ga, In and B, and Q is selected from down array structure:
Compound by chemical formula (1) representative is specifically illustrated by following compounds, but is not restricted to this:
Wherein, the M representative is selected from the divalent metal of Be, Zn, Mg, Cu and Ni, perhaps is selected from the trivalent metal of Al, Ga, In and B; And define in the same chemical formula of Q (1); M is 0 when M is divalent metal, and m is 1 when M is trivalent metal;
R
1To R
4Represent hydrogen independently, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, basic just, n-heptyl, n-octyl, the 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, fluorine, chlorine, trifluoromethyl, the perfluor ethyl, trifluoroethyl, perfluoro propyl, perfluoro butyl, trimethyl silyl, triethylsilyl, the tripropyl silyl, the tri-tert silyl, t-butyldimethylsilyl, the 3,5-dimethylphenyl silyl, the triphenyl silyl, phenyl, xenyl, naphthyl, anthryl, fluorenyl, pyridyl, quinolyl, furyl, thiophenyl, thiazolyl, imidazolyl, azoles base oh, benzofuryl, benzothiazolyl, benzimidazolyl-, benzo is the azoles base oh, dimethylamino, diethylin or diphenylamino;
R
11To R
17And R
21To R
39Represent hydrogen independently, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, basic just, n-heptyl, n-octyl, the 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, fluorine, chlorine, trifluoromethyl, the perfluor ethyl, trifluoroethyl, perfluoro propyl, perfluoro butyl, trimethyl silyl, triethylsilyl, the tripropyl silyl, the tri-tert silyl, t-butyldimethylsilyl, the 3,5-dimethylphenyl silyl, the triphenyl silyl, phenyl, xenyl, naphthyl, fluorenyl, thiophenyl, furyl, dimethylamino, diethylin or diphenylamino;
R
40To R
43Represent hydrogen independently, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, basic just, n-heptyl, n-octyl, the 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, fluorine, chlorine, trifluoromethyl, the perfluor ethyl, trifluoroethyl, perfluoro propyl, perfluoro butyl, trimethyl silyl, triethylsilyl, the tripropyl silyl, the tri-tert silyl, t-butyldimethylsilyl, the 3,5-dimethylphenyl silyl, the triphenyl silyl, phenyl, xenyl, naphthyl, fluorenyl, dimethylamino, diethylin or diphenylamino; With
R
1To R
4, R
11To R
17, R
21To R
39And R
40To R
43Phenyl, xenyl, naphthyl, anthryl, fluorenyl, pyridyl, quinolyl, furyl, thiophenyl, thiazolyl, imidazolyl, azoles base oh, benzofuryl, benzothiazolyl, benzimidazolyl-or benzo oh azoles base can further be replaced by one or more substituting groups, and described substituting group is selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, basic just, n-heptyl, n-octyl, the 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, fluorine, chlorine, cyano group, trifluoromethyl, the perfluor ethyl, trifluoroethyl, perfluoro propyl, perfluoro butyl, phenyl, xenyl, fluorenyl, trimethyl silyl, triethylsilyl, the tripropyl silyl, the tri-tert silyl, t-butyldimethylsilyl, the 3,5-dimethylphenyl silyl, the triphenyl silyl, dimethylamino, diethylin or diphenylamino.
Can specifically illustrate electroluminescent compounds of the present invention by listing in table 1 to the compound in 3, but be not strictly to be confined to this.The compound of listing in table 1 and 3 is that wherein M is the compound of divalent metal, and the compound in the table 2 is that wherein M is the compound of trivalent metal.
Table 1
Table 2
Table 3
Further, the invention provides organic solar batteries, it is characterized in that comprising one or more electroluminescent compounds by chemical formula (1) representative.
In addition, the invention provides electroluminescent device, it comprises first electrode, second electrode and at least one organic layer between described first electrode and second electrode; Wherein said organic layer comprises one or more compounds by chemical formula (1) representative.
Electroluminescent device of the present invention is characterised in that organic layer comprises an electroluminescence layer, it is one or more compounds by chemical formula (1) representative of 2 to 30 weight % that described electroluminescence layer comprises as electroluminescent matrix, content, and one or more electroluminescent doping agents.The electroluminescent doping agent that is applied in the electroluminescent device of the present invention does not have strict restriction, but the available compound of being represented by chemical formula (2) illustrates.
Chemical formula 2
M
1L
2L
3L
4
Wherein, M
1Be selected from the metal of periodictable the 7th, 8,9,10,11,13,14,15 and 16 families, and be preferably selected from Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Te, Au and Ag; And ligand L
2, L
3And L
4Be independently selected from down array structure:
Wherein, R
61And R
62Represent hydrogen, (C1 to C60) alkyl, phenyl or halogen independently;
R
63To R
79Represent hydrogen, (C1 to C60) alkyl, phenyl, three (C1 to C30) alkyl silyl or halogen independently;
R
80To R
83Represent hydrogen, (C1 to C60) alkyl or phenyl independently;
R
84Representative (C1 to C60) alkyl, phenyl or halogen; With
R
61To R
84Alkyl or phenyl can be further replaced by (C1 to C60) alkyl or halogen;
Compound by chemical formula (2) representative can specifically illustrate by having a kind of compound of array structure down, but they are not limited to this.
Electroluminescence layer is meant luminous layer wherein takes place.This layer can be an individual layer, or by with two or more stacked multilayers that form of putting.When using the mixture of matrix-doping agent according to structure of the present invention, because electroluminescent matrix of the present invention, the remarkable improvement of luminous efficiency can be determined.Compare with other substrate material, it provides excellent hole or electron conductivity, and very good stability of material, thereby causes the improvement of device lifetime and luminous efficiency.
Electroluminescent device of the present invention can comprise by the organic electroluminescent compounds of chemical formula (1) representative and be selected from aromatic amine compound or one or more compounds of styryl aromatic amine compound.The example of aromatic amine compound or styryl aromatic amine compound comprises the compound by chemical formula (3) representative, but is not limited thereto:
Wherein, Ar
1And Ar
2Independently representative (C1 to C60) alkyl, (C6 to C60) aryl, (C4 to C60) heteroaryl, (C6 to C60) virtue amino, (C1 to C60) alkylamino, morpholinyl, thiomorpholine for, contain one or more heteroatomic 5 yuan or 6 yuan of Heterocyclylalkyls or (C3 to C60) cycloalkyl of being selected from N, O and S, or Ar
1And Ar
2Can be by (C3 to C60) alkylene or connection formation of (C3 to C60) alkenylene alicyclic ring or monocyclic aromatic rings or the many cyclophanes ring that is with or without fused rings; And Ar
1And Ar
2Aryl, heteroaryl, virtue amino or Heterocyclylalkyl can further be replaced by one or more substituting groups, and described substituting group is selected from halogen, (C1 to C60) alkyl, (C2 to C60) alkenyl, (C2 to C60) alkynyl, (C6 to C60) aryl, (C4 to C60) heteroaryl, contain and be selected from N, one or more heteroatomic 5 yuan or 6 yuan of Heterocyclylalkyls of O and S, (C3 to C60) cycloalkyl, three (C1 to C60) alkyl silyl, two (C1 to C60) alkyl (C6 to C60) aryl silyl, three (C6 to C60) aryl silyl, adamantyl (adamantly), (C7 to C60) bicyclic alkyl, (C1 to C60) alkoxyl group, cyano group, (C1 to C60) alkylamino, (C6 to C60) virtue is amino, (C6 to C60) aryl (C1 to C60) alkyl, (C6 to C60) aryloxy, (C6 to C60) arylthio, (C1 to C60) alkoxy carbonyl, carbonyl, nitro and hydroxyl;
Ar
3Representative (C6 to C60) aryl, (C5 to C60) heteroaryl or (C6 to C60) virtue are amino; Ar
3Aryl, heteroaryl or fragrant amino can further be replaced by one or more substituting groups, and described substituting group is selected from halogen, (C1 to C60) alkyl, (C6 to C60) aryl, (C4 to C60) heteroaryl, contain and be selected from N, one or more heteroatomic 5 yuan or 6 yuan of Heterocyclylalkyls of O and S, (C3 to C60) cycloalkyl, three (C1 to C60) alkyl silyl, two (C1 to C60) alkyl (C6 to C60) aryl silyl, three (C6 to C60) aryl silyl, adamantyl (adamantly), (C7 to C60) bicyclic alkyl, (C2 to C60) alkenyl, (C2 to C60) alkynyl, cyano group, (C1 to C60) alkylamino, (C6 to C60) virtue is amino, (C6 to C60) aryl (C1 to C60) alkyl, (C6 to C60) aryloxy, (C6 to C60) arylthio, (C1 to C60) alkoxy carbonyl, carbonyl, nitro and hydroxyl; With
G is 1 to 4 integer.
More specifically, aromatic amine compound or styryl aromatic amine compound can illustrate by following compounds, but are not limited thereto.
Further, in electroluminescent device of the present invention, except organic electroluminescent compounds by chemical formula (1) representative, electroluminescence layer can further comprise one or more metals, and described metal is selected from the group of being made up of the transition metal in the organo-metallic of the 1st family, the 2nd family, the 4th cycle and the 5th cycle, lanthanide series metal and d-transition element.Except the EL layer, organic layer also can comprise charge generation layer.
Electroluminescent device can be specially has the independently dot structure of light-emitting mode, wherein, organic electroluminescence device comprise by chemical formula (1) representative, as the EL compound of sub-pixel, one or more sub-pixels form pattern in a parallel manner simultaneously, and described one or more sub-pixels contain one or more compounds that are selected from aromatic amine compound and styryl aromatic amine compound.
In addition, electroluminescence layer can include organic compounds or organometallic compound, and described compound has the electroluminescent peak simultaneously in being no more than the wavelength of 560nm.These compounds can be illustrated by the compound of chemical formula (4) to one of (9) representative, but are not limited thereto.
In chemical formula (4), Ar
10And Ar
20Represent (C1 to C60) alkyl independently, (C6 to C60) aryl, (C4 to C60) heteroaryl, contain and be selected from N, one or more heteroatomic 5 yuan or 6 yuan of Heterocyclylalkyls of O and S, (C3 to C60) cycloalkyl, three (C1 to C60) alkyl silyl, two (C1 to C60) alkyl (C6 to C60) aryl silyl, three (C6 to C60) aryl silyl, adamantyl (adamantly), (C7 to C60) bicyclic alkyl, (C2 to C60) alkenyl, (C2 to C60) alkynyl, (C1 to C60) alkoxyl group, cyano group, (C1 to C60) alkylamino, (C6 to C60) virtue is amino, (C6 to C60) aryl (C1 to C60) alkyl, (C6 to C60) aryloxy, (C6 to C60) arylthio, (C1 to C60) alkoxy carbonyl, carbonyl, nitro and hydroxyl, or Ar
10And Ar
20Can be by (C3 to C60) alkylene or (C3 to the C60) alkenylene that is with or without fused rings, connect adjacent substituting group and form alicyclic ring or monocyclic aromatic rings or many cyclophanes ring;
Ar
10And Ar
20Alkyl, alkenyl, alkynyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, the aryl silyl, the alkyl silyl, alkylamino or virtue are amino, perhaps (C3 to the C60) alkylene by being with or without fused rings or (C3 to C60) alkenylene connect adjacent substituting group and the fused rings that forms thus, can further be replaced by one or more substituting groups, described substituting group is selected from halogen, (C1 to C60) alkyl, (C6 to C60) aryl, (C4 to C60) heteroaryl, contain and be selected from N, one or more heteroatomic 5 yuan or 6 yuan of Heterocyclylalkyls of O and S, (C3 to C60) cycloalkyl, three (C1 to C60) alkyl silyl, two (C1 to C60) alkyl (C6 to C60) aryl silyl, three (C6 to C60) aryl silyl, adamantyl (adamantly), (C7 to C60) bicyclic alkyl, (C2 to C60) alkenyl, (C2 to C60) alkynyl, (C1 to C60) alkoxyl group, cyano group, (C1 to C60) alkylamino, (C6 to C60) virtue is amino, (C6 to C60) aryl (C1 to C60) alkyl, (C6 to C60) aryloxy, (C6 to C60) arylthio, (C1 to C60) alkoxy carbonyl, carbonyl, nitro and hydroxyl;
Ar
30Representative (C6 to C60) virtue amino, (C6 to C60) arylidene, (C4 to C60) heteroarylidene or arylidene with following structure:
Wherein, Ar
40Representative (C6 to C60) arylidene or (C4 to C60) heteroarylidene;
Ar
30Arylidene, heteroarylidene and fragrant amino can further be selected from one or more following substituting groups and be replaced: halogen, (C1 to C60) alkyl, (C6 to C60) aryl, (C4 to C60) heteroaryl, contain and be selected from N, one or more heteroatomic 5 yuan or 6 yuan of Heterocyclylalkyls of O and S, (C3 to C60) cycloalkyl, three (C1 to C60) alkyl silyl, two (C1 to C60) alkyl (C6 to C60) aryl silyl, three (C6 to C60) aryl silyl, adamantyl (adamantly), (C7 to C60) bicyclic alkyl, (C2 to C60) alkenyl, (C2 to C60) alkynyl, (C1 to C60) alkoxyl group, cyano group, (C1 to C60) alkylamino, (C6 to C60) virtue is amino, (C6 to C60) aryl (C1 to C60) alkyl, (C6 to C60) aryloxy, (C6 to C60) arylthio, (C1 to C60) alkoxy carbonyl, carbonyl, nitro and hydroxyl;
H is 1 to 4 integer;
I is 1 to 4 integer; And
J is 0 or 1 integer.
Chemical formula 5
In chemical formula (5), R
501To R
504Represent hydrogen independently, halogen, (C1 to C60) alkyl, (C6 to C60) aryl, (C4 to C60) heteroaryl, contain and be selected from N, one or more heteroatomic 5 yuan or 6 yuan of Heterocyclylalkyls of O and S, (C3 to C60) cycloalkyl, three (C1 to C60) alkyl silyl, two (C1 to C60) alkyl (C6 to C60) aryl silyl, three (C6 to C60) aryl silyl, adamantyl (adamantly), (C7 to C60) bicyclic alkyl, (C2 to C60) alkenyl, (C2 to C60) alkynyl, (C1 to C60) alkoxyl group, cyano group, (C1 to C60) alkylamino, (C6 to C60) virtue is amino, (C6 to C60) aryl (C1 to C60) alkyl, (C6 to C60) aryloxy, (C6 to C60) arylthio, (C1 to C60) alkoxy carbonyl, carbonyl, nitro or hydroxyl, or R
501To R
504(C3 to C60) alkylene that can be by being with or without fused rings or (C3 to C60) thus alkenylene connects adjacent substituting group forms alicyclic ring, monocyclic aromatic rings or many cyclophanes ring; With
R
501To R
504Alkyl, alkenyl, alkynyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl, the aryl silyl, the alkyl silyl, alkylamino or virtue are amino, perhaps (C3 to the C60) alkylene by being with or without fused rings or (C3 to C60) alkenylene connect adjacent substituting group and the fused rings that forms thus, can further be replaced by one or more substituting groups, described substituting group is selected from halogen, (C1 to C60) alkyl, (C6 to C60) aryl, (C4 to C60) heteroaryl, contain and be selected from N, one or more heteroatomic 5 yuan or 6 yuan of Heterocyclylalkyls of O and S, (C3 to C60) cycloalkyl, three (C1 to C60) alkyl silyl, two (C1 to C60) alkyl (C6 to C60) aryl silyl, three (C6 to C60) aryl silyl, adamantyl (adamantly), (C7 to C60) bicyclic alkyl, (C2 to C60) alkenyl, (C2 to C60) alkynyl, (C1 to C60) alkoxyl group, cyano group, (C1 to C60) alkylamino, (C6 to C60) virtue is amino, (C6 to C60) aryl (C1 to C60) alkyl, (C6 to C60) aryloxy, (C6 to C60) arylthio, (C1 to C60) alkoxy carbonyl, carbonyl, nitro and hydroxyl.
Chemical formula 6
Chemical formula 8
In chemical formula (7) and (8), R
101And R
102Independently representative (C6 to C60) aryl, (C4 to C60) heteroaryl, contain one or more heteroatomic 5 yuan or 6 yuan of Heterocyclylalkyls or (C3 to C60) cycloalkyl of being selected from N, O and S; And R
101And R
102Aryl or heteroaryl can further be replaced by one or more substituting groups, described substituting group is selected from (C1 to C60) alkyl, halo (C1 to C60) alkyl, (C1 to C60) alkoxyl group, (C3 to C60) cycloalkyl, (C6 to C60) aryl, (C4 to C60) heteroaryl, halogen, cyano group, three (C1 to C60) alkyl silyl, two (C1 to C60) alkyl (C6 to C60) aryl silyl and three (C6 to C60) aryl silyl; And R
103To R
106Represent hydrogen, (C1 to C60) alkyl, (C1 to C60) alkoxyl group, halogen, (C4 to C60) heteroaryl, (C5 to C60) cycloalkyl or (C6 to C60) aryl; And R
103To R
106Heteroaryl, cyclophane base or aryl can further be replaced by one or more substituting groups, described substituting group is selected from and is with or without (C1 to C60) alkyl, (C1 to C60) alkoxyl group, (C3 to C60) cycloalkyl, halogen, cyano group, three (C1 to C60) alkyl silyl, two (C1 to C60) alkyl (C6 to C60) aryl silyl and three (C6 to C60) aryl silyl that halogen replaces.
Chemical formula 9
In chemical formula (9), B and D represent chemical bond independently or are with or without one or more substituent (C6 to C60) arylidene, and described substituting group is selected from (C1 to C60) alkyl, (C1 to C60) alkoxyl group, (C6 to C60) aryl, (C5 to C60) heteroaryl and halogen;
Ar
100And Ar
300Representative is selected from down aryl or (C4 to C60) heteroaryl of array structure independently; And Ar
100And Ar
300Aryl or heteroaryl one or more substituting groups that can further be selected from (C1 to C60) alkyl, (C1 to C60) alkoxyl group, (C6 to C60) aryl and (C4 to C60) heteroaryl replace:
Wherein, R
311, R
312, R
313And R
314Represent hydrogen, (C1 to C60) alkyl or (C6 to C60) aryl independently, (C3 to C60) alkylene that perhaps can be by being with or without fused rings or (C3 to C60) thus alkenylene connects adjacent substituting group forms alicyclic ring, monocyclic aromatic rings or many cyclophanes ring;
Ar
200Representative (C6 to C60) arylidene or (C4 to C60) heteroarylidene are preferably phenylene, naphthylidene, anthrylene, fluorenylidene, phenanthrylene, inferior four also phenyl (tetracenylene), naphthacenylene, Asia
Base (chrysenylene), Asia five and phenyl (pentacenylene), inferior pyrrole base (pyrenylene), heteroarylidene or the chemical group of representing by following array structure, and Ar
200Arylidene or heteroarylidene one or more substituting groups that can further be selected from (C1 to C60) alkyl, (C1 to C60) alkoxyl group, (C6 to C60) aryl and (C4 to C60) heteroaryl and halogen replace;
Wherein, R
321, R
322, R
323And R
324Represent hydrogen, (C1 to C60) alkyl, (C6 to C60) aryl, (C6 to C60) aryl, (C4 to C60) heteroaryl or halogen independently, (C3 to C60) alkylene that perhaps can be by being with or without fused rings or (C3 to C60) thus alkenylene connects adjacent substituting group forms alicyclic ring, monocyclic aromatic rings or many cyclophanes ring.
Organic compound or organometallic compound that the wavelength at EL peak is no more than 560nm can specifically illustrate by following compound, but are not limited thereto.
In electroluminescent device of the present invention, one or more layers (being called hereinafter, " upper layer ") that preferably will be selected from chalcogenide layer, metal halide and metal oxide, be placed on the internal surface of at least one side of pair of electrodes.Particularly, preferably the chalcogenide layer of silicon and aluminum metal (comprising oxide compound) is placed on the anode surface of EL medium layer, metal halide or metal oxide layer is placed on the cathode surface of EL medium layer.As a result, can obtain operational stability.
The example of chalkogenide preferably includes SiO
x(1≤X≤2), AlO
x(11≤X≤1.5), SiON, SiAlON etc.The example of metal halide preferably includes LiF, MgF
2, CaF
2, lanthanum fluoride etc.The example of metal oxide preferably includes Cs
2O, Li
2O, MgO, SrO, BaO, CaO etc.
In organic electroluminescence device of the present invention, also preferably place electric transmission compound and the mixing zone of reduction doping agent or the mixing zone of hole transport compound and oxidant dopant of as above making at least one surface of pair of electrodes.Therefore, the electric transmission compound is reduced to negatively charged ion, so that has promoted to inject and transmission from the mixing zone to the electronics of EL medium.In addition, because the hole transport compound is oxidized to positively charged ion, promoted to inject and transmission from the mixing zone to the hole of EL medium.Preferred oxidant dopant comprises various Lewis acids and is subjected to main compound.Preferred reduction doping agent comprises basic metal, alkali metal compound, alkaline-earth metal, rare earth metal and their mixture.
Beneficial effect
In OLED, be used as the electroluminescent compounds of the present invention of the substrate material of phosphor material, can significantly reduce operating voltage and increase current efficiency, thereby make efficiency factor increase greatly.
Description of drawings
Fig. 1 is the cross-sectional view strength of OLED.
The explanation of the symbol of accompanying drawing significant part
1: glass
2: transparency electrode
3: hole injection layer
4: hole transmission layer
5: electroluminescence layer
6: electron transfer layer
7: electron injecting layer
The 8:Al negative electrode
Embodiment
The present invention is by reference example and preparation embodiment, to new electroluminescent compounds of the present invention, its preparation method and adopt the characteristics of luminescence of its device to do to further describe, described in a word embodiment and preparation embodiment only are used for explanation, and do not tend to limit the scope of the invention.
The preparation of preparation embodiment 1-compound (1)
The preparation of compound (501)
In dimethyl ethylene glycol (200mL) and ethanol (100mL), dissolving 5-bromo-2-hydroxy benzaldehyde (20.0g, 99.5mmol), (13.4g, 109.5mmol), four (palladium (0) triphenyl phosphines) are (Pd (pph (tetrakispalladium) for phenyl-boron dihydroxide (phenylboronic acid)
3)
4) (5.8g, 5.0mmol).Behind the wet chemical that wherein adds 2M (132mL), the gained mixture stirred 4 hours under 90 ℃ of backflows.After reaction finishes, with water (100mL) thus add and finish reaction in the reaction mixture.(200mL) extracts described mixture with ethyl acetate, and under the pressure that reduces drying composite.By silica gel column chromatography (normal hexane: MC=1:5) purifying, obtain compound (501) (12.0g, 61.0mmol).
The preparation of compound (502)
1, dissolving 2-aminothiophenol in the 4-diox (12mL) (3.8g, 30.2mmol) and compound (501) (5.0g, 25.2mmol), gained solution is in the stirring 12 hours down of 100 ℃ of negative pressure.After reaction finishes, reaction mixture is cooled to room temperature, with methylene dichloride (100mL) and water (100mL) extraction, dry under the pressure that reduces then.By silica gel column chromatography (normal hexane: MC=3:1) purifying, obtain compound (502) (4.5g, 4.8mmol).
The preparation of compound (1)
Dissolved compound (502) in ethanol (100mL) (4.5g, 14.8mmol) and sodium hydroxide (0.6g, 14.8mmol).After the gained solution stirring 30 minutes, with Zn (CH
3COO)
22H
2(1.8g 8.2mmol) slowly adds wherein O.Described then mixture at room temperature stirred 12 hours.After reaction finished, water (200mL), ethanol (200mL) and hexane (200mL) washed described reaction mixture successively, and be dry under the pressure that reduces then, thereby obtain the compound (1) (4.5g, 6.7mmol, 45%) of title.
The preparation of preparation embodiment 2-compound (160)
The preparation of compound (503)
Dissolving 5-indoline iodine 2 in dimethylene ethylene glycol (600mL), the 3-diketone (10.0g, 36.6mmol) and phenyl-boron dihydroxide (5.4g, 43.9mmol), and with four (palladium (0) triphenyl phosphine) (Pd (pph3) 4) (2.1g, 1.8mmol) and 2M sodium bicarbonate aqueous solution (120mL) add wherein.The gained mixture stirred 12 hours under refluxing.After reaction finishes, remove solvent.(120mL) adds in the resistates with 5% aqueous sodium hydroxide solution, and described mixture at room temperature stirs.With this aqueous solution of dichloromethane extraction.Contain water section and merged, then to wherein adding 30% aqueous hydrogen peroxide (100mL).The gained mixture is heated to 50 ℃ and stirred 30 minutes.After being cooled to room temperature, be 4 thereby the 1N spirit of salt aqueous solution is added above-mentioned aqueous solution adjusting pH lentamente.The solid that filter to generate, under the pressure that reduces dry and obtain compound (503) (5.5g, 26.0mmol).
The preparation of compound (504)
(7.1g 33.3mmol), at room temperature stirs described solution to dissolved compound (503) in water (18mL) and dense spirit of salt (7mL) then.After 10 minutes, temperature is reduced to 0 ℃, adds the SODIUMNITRATE (NaNO that is dissolved in (10mL) in the water then lentamente
3) (2.3g, 33.3mmol).When then temperature being remained 0 ℃, stir described mixture.In another reaction vessel, with nine hydrated sodium sulfide (Na
2S9H
2O) (9.6g, 39.9mmol) and sulphur (1.3g 39.9mmol) is dissolved in the water (10mL), then 10M aqueous sodium hydroxide solution (4mL) is added in the above-mentioned solution.At 0 ℃ the gained mixture is added in the above-mentioned reaction mixture, be heated to room temperature, be stirred to no longer then and produce till the gas.After reaction finishes, generate solid thereby add dense spirit of salt, described solid is then under reduced pressure collected by filtration.The gained solid adds sodium bicarbonate (NaHCO to
3) in the aqueous solution (85mL), and under refluxing, stirred 20 minutes.After being cooled to room temperature, remove undissolved solid (impurity), dense spirit of salt is added in the described aqueous solution, to form solid once more.Then the solid that is under reduced pressure obtained by filtration is added in the ethanol (30mL), and under refluxing, stirred 20 minutes.Remove undissolved solid (impurity), filtrate is concentrated.Add zinc (2.2g, 33.3mmol) and Glacial acetic acid (30mL), the stirring 48 hours under refluxing of gained mixture.When reaction finishes, reaction mixture is cooled to room temperature, collect the solid that generates, and it is added in the aqueous sodium hydroxide solution (63mL) of 5M.Under refluxing, stir after 30 minutes, remove undissolved solid (impurity), a small amount of dense spirit of salt is added in the described aqueous solution, with souring soln.Then collect the solid that generates, add to then in the ethanol (20mL), the gained mixture stirred 30 minutes under refluxing.Remove undissolved solid (impurity), concentrated filtrate and obtain compound (504) (1.8g, 7.6mmol).
The preparation of compound (505)
In a reaction vessel, under refluxing in 140 ℃ of agitate compounds (504) (5.0g, 21.7mmol), the 2-aminothiophenol (2.1mL, 19.5mmol) and Tripyrophosphoric acid (20g) 24 hours.After reaction finished, mixture was cooled to room temperature, and is by the saturated aqueous sodium hydroxide solution of slow interpolation that pH regulator is extremely neutral.Under reduced pressure filter the solid that generates, thereby obtain solid.The solid that so obtains with washing with alcohol, and filter and obtain compound (505) (5.4g, 17.1mmol).
The preparation of compound (160)
In ethanol (100mL), dissolved compound (505) (5.0g, 15.6mmol) and sodium hydroxide (0.6g, 15.6mmol), stirred solution 30 minutes.With Zn (CH
3COO)
22H
2(1.9g 8.7mmol) slowly adds in the solution O, and stirs the mixture 12 hours.Then, water (200mL), ethanol (200mL) and hexane (200mL) washing reaction mixture successively, drying under reduced pressure then, thus obtain the compound (160) (7.1g, 10.1mmol, 65%) of title.
Preparation embodiment 3-compound (319) preparation
In chloroform (50mL)/Virahol (150mL), dissolved compound (502) (4.5g, 14.8mmol) and AIP (3.0g, 14.8mmol), solution stirred 3 hours down at 60 ℃.When solution becomes was limpid, (3.0g, 17.8mmol), mixture stirred 3 hours down in 80 ℃ under refluxing to wherein adding the 4-phenylphenol.Further (4.5g, 14.8mmol), the gained mixture stirred 12 hours under refluxing to wherein adding compound (502).After reaction finished, reaction mixture was cooled to room temperature, under reduced pressure filtered the solid that generates.Then use Virahol (500mL), methyl alcohol (300mL) and ether (250mL) washing solid in turn, thereby obtain title compound (319) (3.8g, 7.6mmol, 51%).
According to the identical process of preparation embodiment 1 to 3, preparation compound (1) is to (408), they
1HNMR and MS/FAB data are shown in Table 4.
Table 4
Embodiment 1 to 23---use the manufacturing of the OLEDs of EL compound of the present invention
The EL compound of the application of the invention is made the OLED device as substrate material.The cross-sectional view strength of OLED is shown among Fig. 1.
At first, (supersound washing is carried out with trieline, acetone, ethanol and distilled water in 15 Ω/) (2) to the transparency electrode ito thin film that is obtained by the glass that is used for OLED (being produced by Samsung Corning) in turn, is stored in the Virahol before use then.
Then, ito substrate is assemblied in the substrate folder of vacuum vapor deposition device, 4,4 ', 4 " three (N, N-(2-naphthyl)-phenyl amino) triphenylamine (2-TNATA) is placed in the pond of vacuum vapor deposition device, described equipment is vented to have in the chamber the highest by 10
-6The vacuum of torr.Electric current is applied on the pond with evaporation 2-TNATA, thereby the vapor deposition of the thick hole injection layer of 60nm (3) is provided on ito substrate.
Then, the N that in another pond of vacuum deposition equipment, packs into, N '-two (Alpha-Naphthyl)-N, N '-phenylbenzene-4,4 '-diamines (NPB), this pond is applied electric current with evaporation NPB, thereby the vapor deposition of the thick hole transmission layer of 20nm (4) is provided on hole injection layer.
In a pond of vacuum vapor deposition device, to pack into as the compound of the present invention of substrate material, this compound passes through 10
-6Vacuum-sublimation under the torr and purify (for example, compound 1), and EL doping agent ((pip for example
2Ir (acac)) packs in another pond.Two kinds of materials evaporate under different rates, thereby carry out the vapor deposition of the doping of 4 to 10mol% concentration and the electroluminescence layer (5) that 30nm is thick on hole transmission layer.
Then, three (oxine) aluminium (III) is the electron transfer layer (6) of thickness 20nm by vapor deposition (Alq), and quinophenol (oxine) lithium (lithium quinolate) is 1 to 2nm thick electron injecting layer (7) by vapor deposition (Liq) then.After this, come the thick Al negative electrode (8) of vapor deposition 150nm, thereby make OLED by using another vacuum vapor deposition device.
Comparative Examples 1
Comparative Examples 1---use the manufacturing of the OLED device of traditional E L material
Except replacing with two (2-methyl-8-quinoline generation) (p-phenyl phenol) aluminium (III) EL compound of the present invention packs in another pond of vacuum vapor deposition device as the EL substrate material, make the OLED device according to the step identical with embodiment 1.
The Performance Evaluation of the OLED device of tentative embodiment 1-manufacturing
Comprise operating voltage and specific power that make, that comprise the OLEDs of traditional E L compound in the OLEDs of embodiment 1 to 23 of EL compound of the present invention and the Comparative Examples 1, at 1000cd/m
2Measured down, the results are shown in the table 5.
5 illustrated that the EL compound that the confirmable the present invention of being researches and develops shows than the more excellent performance of traditional E L material at aspect of performance by the electroluminescent properties of the EL compound of the present invention research and development by tabulating down.
Table 5
| Substrate material | The EL material | Operating voltage (V) @1000 cd/m 2 | Specific power (1m/W) @1000cd/m 2 | The EL color | |
| Embodiment 1 | 1 | (piq) 2Ir(acac) | 5.6 | 4.4 | Red |
| Embodiment 2 | 3 | (piq) 2Ir(acac) | 5.2 | 4.7 | |
| Embodiment | |||||
| 3 | 41 | (piq) 2Ir(acac) | 5.1 | 4.8 | |
| Embodiment | |||||
| 4 | 47 | (piq) 2Ir(acac) | 5.1 | 4.4 | Red |
| Embodiment 5 | 87 | (piq) 2Ir(acac) | 5.4 | 4.0 | Red |
| Embodiment 6 | 109 | (piq) 2Ir(acac) | 4.9 | 4.4 | |
| Embodiment | |||||
| 7 | 110 | (piq) 2Ir(acac) | 5.2 | 4.3 | Red |
| Embodiment 8 | 115 | (piq) 2Ir(acac) | 6.1 | 4.3 | Red |
| Embodiment 9 | 144 | (piq) 2Ir(acac) | 6.2 | 4.7 | Red |
| Embodiment 10 | 160 | (piq) 2Ir(acac) | 6.2 | 4.2 | Red |
| Embodiment 11 | 162 | (piq) 2Ir(acac) | 5.2 | 3.9 | Red |
| Embodiment 12 | 165 | (piq) 2Ir(acac) | 5.1 | 4.5 | Red |
| Embodiment 13 | 224 | (piq) 2Ir(acac) | 5.3 | 4.2 | Red |
| Embodiment 14 | 252 | (piq) 2Ir(acac) | 5.3 | 4.3 | Red |
| Embodiment 15 | 254 | (piq) 2Ir(acac) | 5.7 | 4.0 | Red |
| Embodiment 16 | 269 | (piq) 2Ir(acac) | 5.3 | 4.2 | Red |
| Embodiment 17 | 315 | (piq) 2Ir(acac) | 5.8 | 4.3 | Red |
| Embodiment 18 | 318 | (piq) 2Ir(acac) | 5.4 | 4.1 | Red |
| Embodiment 19 | 335 | (piq) 2Ir(acac) | 7.0 | 3.4 | Red |
| Embodiment 20 | 336 | (piq) 2Ir(acac) | 6.8 | 3.8 | Red |
| Embodiment 21 | 377 | (piq) 2Ir(acac) | 6.6 | 3.5 | Red |
| Embodiment 22 | 379 | (piq) 2Ir(acac) | 6.3 | 3.5 | Red |
| Embodiment 23 | 408 | (piq) 2Ir(acac) | 5.1 | 4.7 | Red |
| Comparative Examples 1 | BAlq | (piq) 2Ir(acac) | 7.5 | 2.6 | Red |
The electroluminescent properties that can be determined the title complex that the present invention researches and develops by table 5 is better than traditional material.
Especially, compare, will be attached to ligand L such as one or more substituting groups of methyl, phenyl and naphthyl with the Comparative Examples 1 that adopts traditional E L material
1On, the OLEDs that has excellent current capability and reduce the 1V operating voltage at least is provided.Because the EL performance of their excellences is compared with the device of Comparative Examples 1, compound of the present invention also provides high at least 1.6 times specific power.Not only at X=O, and under the situation of X=S, device of the present invention is worked under the voltage than the low 1V at least of the device that uses traditional material, and demonstrates the specific power of high at least 1.3lm/W.
In particular, in embodiment 6, device is worked under the voltage than the low 2.6V of the device of Comparative Examples 1; In embodiment 3, device is at 1000cd/m
2Show down the operating voltage of 5.1V and the specific power of 4.8lm/W.
Therefore, adopt electroluminescent compounds of the present invention to show the excellent electroluminescent properties and the operating voltage of reduction, cause specific power to increase by 0.8～2.2lm/W, thereby improve power loss as the device of substrate material.
Claims (20)
1. electroluminescent compounds, it is represented by chemical formula (1):
Chemical formula 1
L
1L
1M(Q)
m
Wherein, ligand L
1Have structure as follows:
M represents divalence or trivalent metal;
M is 0 when M is divalent metal, and m is 1 when M is trivalent metal;
Q representative (C6 to C60) aryloxy or three (C6 to C60) aryl silyl, the aryloxy of Q or diarye silyl can further be replaced by straight or branched (C1 to C60) alkyl or (C1 to C60) aryl;
When X represented O, ring A was selected from down array structure:
When X represented S, ring A was selected from down array structure:
R
1To R
4Represent hydrogen, (C1 to C60) alkyl, halogen, cyano group, (C3 to C60) cycloalkyl, (C6 to C60) aryl, (C4 to C60) heteroaryl, single or two (C1 to C30) alkylamino, single or two (C6 to C30) virtue amino, three (C1 to C30) alkyl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl or three (C6 to C30) aryl silyl independently, maybe can pass through (C3 to C12) alkylene or (C3 to C12) thereby the adjacent substituting group formation fused rings of alkenylene connection;
R
11To R
17Represent hydrogen, (C1 to C60) alkyl, (C6 to C60) aryl, (C4 to C60) heteroaryl, three (C1 to C30) alkyl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl, three (C6 to C30) aryl silyl, single or two (C1 to C30) alkylamino, single or two (C6 to C30) virtue amino, cyano group or halogen independently, or R
13To R
16Can pass through (C3 to C12) alkylene or (C3 to C12) thereby the adjacent substituting group formation fused rings of alkenylene connection;
R
21To R
39Represent hydrogen, (C1 to C60) alkyl, (C6 to C60) aryl, (C4 to C60) heteroaryl, three (C1 to C30) alkyl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl, three (C6 to C30) aryl silyl, single or two (C1 to C30) alkylamino, single or two (C6 to C30) virtue amino, cyano group or halogen independently;
R
1To R
4Alkyl, aryl or heteroaryl, the fused rings that perhaps connects adjacent substituting group and form thus by (C3 to C12) alkylene or (C3 to C12) alkenylene, can further be replaced by one or more substituting groups, described substituting group is selected from (C1 to C60) alkyl, (C1 to the C60) alkyl that is replaced by halogen, (C6 to C60) aryl, three (C1 to C30) aryl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl, three (C6 to C30) aryl silyl, single or two (C1 to C30) alkylamino, single or two (C6 to C30) virtue is amino, cyano group and halogen;
R
11To R
17And R
21To R
39Alkyl, aryl or heteroaryl can further be replaced (C1 to C60) alkyl, halogen, (C6 to C60) aryl, single or two (C1 to C30) alkylamino, single or two (C6 to C30) virtue amino, three (C1 to C30) aryl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl, three (C6 to C30) aryl silyl and cyano group that described substituting group is selected from (C1 to C60) alkyl, is replaced by halogen by one or more substituting groups.
2. electroluminescent compounds according to claim 1, wherein ligand L
1Be selected from down array structure:
R wherein
1, R
2, R
3And R
4Have with the definition in the Chemical formula 1;
R
11To R
16(C1 to C60) alkyl, phenyl, naphthyl, xenyl, fluorenyl, three (C1 to C30) alkyl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl, three (C6 to C30) aryl silyl, two (C1 to C30) alkylamino, two (C6 to the C30) virtue of representing hydrogen, (C1 to C60) alkyl, halogen independently, being replaced by halogen is amino, thiophenyl or furyl;
R
17Representative (C1 to C60) alkyl, phenyl or naphthyl;
R
21And R
22(C1 to C60) alkyl, phenyl, naphthyl, xenyl, fluorenyl, three (C1 to C30) alkyl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl, three (C6 to C30) aryl silyl, two (C1 to C30) alkylamino, two (C6 to the C30) virtue of representing hydrogen, (C1 to C60) alkyl, halogen independently, being replaced by halogen is amino, thiophenyl or furyl;
R
23Representative (C1 to C60) alkyl, phenyl or naphthyl;
R
24To R
39(C1 to C60) alkyl, phenyl, naphthyl, xenyl, fluorenyl, three (C1 to C30) alkyl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl, three (C6 to C30) aryl silyl, two (C1 to C30) alkylamino, two (C6 to the C30) virtue of representing hydrogen, (C1 to C60) alkyl, halogen independently, being replaced by halogen is amino, thiophenyl or furyl;
R
40To R
43(C1 to C60) alkyl, phenyl, naphthyl, xenyl, fluorenyl, three (C1 to C30) alkyl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl, three (C6 to C30) aryl silyl, two (C1 to C30) alkylamino, the fragrant amino of two (C6 to C30) or the halogen representing hydrogen, (C1 to C60) alkyl independently, replaced by halogen; With
R
11To R
17, R
21To R
39And R
40To R
43Phenyl, naphthyl, xenyl, fluorenyl, thiophenyl or furyl can further be replaced by one or more substituting groups, described substituting group is selected from (C1 to C60) alkyl, halogen, phenyl, naphthyl, fluorenyl, three (C1 to C30) alkyl silyl, two (C1 to C30) alkyl (C6 to C30) aryl silyl, three (C6 to C30) aryl silyl, two (C1 to C30) alkylamino or two (C6 to C30) virtue is amino.
3. electroluminescent compounds according to claim 2, wherein ligand L
1Be selected from following structure:
Wherein, R
1To R
4Represent hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, chlorine, fluorine, phenyl, xenyl, naphthyl, fluorenyl, thiophenyl, trimethyl silyl, triphenyl silyl, t-butyldimethylsilyl, dimethylamino, diethylin or diphenylamino independently, get rid of wherein R
1, R
2, R
3And R
4All represent simultaneously the situation of hydrogen;
R
11And R
12Represent methylidene, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, trimethyl silyl, triphenyl silyl, phenyl, xenyl, naphthyl or fluorenyl independently;
R
13To R
16Represent methylidene, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, trimethyl silyl, triphenyl silyl, phenyl, xenyl, naphthyl or fluorenyl independently;
R
17Represent methylidene, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, phenyl or naphthyl;
R
21And R
22Represent hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, fluorine, trifluoromethyl, phenyl, naphthyl, xenyl, trimethyl silyl, triphenyl silyl, dimethylamino, diphenylamino, thiophenyl or furyl independently;
R
25And R
26Represent hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, fluorine, trifluoromethyl, phenyl, naphthyl, xenyl, trimethyl silyl, triphenyl silyl, dimethylamino, diphenylamino, thiophenyl or furyl independently; With
R
1, R
2, R
3, R
4, R
11, R
12, R
13, R
14, R
15, R
16, R
17, R
21, R
22, R
25And R
26Phenyl, xenyl, naphthyl, fluorenyl and thiophenyl can further be replaced by one or more substituting groups, described substituting group is selected from fluorine, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, TMS, tertiary butyl dimethylsilyl, phenyl, naphthyl, fluorenyl, dimethylamino, diethylin and diphenylamino.
4. electroluminescent compounds according to claim 1, wherein M is the divalent metal that is selected from Be, Zn, Mg, Cu and Ni, perhaps is selected from the trivalent metal of Al, Ga, In and B.
5. electroluminescent compounds according to claim 1, wherein Q is selected from down array structure:
6. electroluminescent compounds according to claim 1, it is selected from following compounds:
7. electroluminescent device, it comprises each described electroluminescent compounds of claim 1 to 6.
8. electroluminescent device according to claim 7, wherein said electroluminescent compounds is used as the substrate material of electroluminescence layer.
9. electroluminescent device, it comprises:
First electrode;
Second electrode; With
At least one organic layer between described first electrode and second electrode;
Wherein said organic layer comprises each described one or more electroluminescent compounds of claim 1 to 6.
10. electroluminescent device according to claim 9, wherein said organic layer comprises electro-luminescent zones, described electro-luminescent zones comprises described one or more electroluminescent compounds of claim 1 to 6 and one or more electroluminescent doping agents.
11. electroluminescent device according to claim 10, wherein said electroluminescent doping agent are the compounds of chemical formula (2) representative:
Chemical formula 2
M
1L
2L
3L
4
Wherein, M
1Be selected from the metal of periodictable the 7th, 8,9,10,11,13,14,15 and 16 families, and ligand L
2, L
3And L
4Be independently selected from down array structure:
Wherein, R
61And R
62Represent hydrogen, (C1 to C60) alkyl, phenyl or halogen independently;
R
63To R
79Represent hydrogen, (C1 to C60) alkyl, phenyl, three (C1 to C30) alkyl silyl or halogen independently;
R
80To R
83Represent hydrogen, (C1 to C60) alkyl or phenyl independently;
R
84Representative (C1 to C60) alkyl, phenyl or halogen; With
R
61To R
84Alkyl or phenyl can be further replaced by (C1 to C60) alkyl or halogen.
12. electroluminescent device according to claim 11, wherein said electroluminescent doping agent is selected from following compounds:
13. electroluminescent device according to claim 9, wherein said organic layer comprise one or more compounds that are selected from aromatic amine compound and styryl aromatic amine compound.
14. electroluminescent device according to claim 9, wherein said organic layer comprises one or more metals, and described metal is selected from the group of being made up of the transition metal in the organo-metallic of the 1st family, the 2nd family, the 4th cycle and the 5th cycle, lanthanide series metal and d-transition element.
15. electroluminescent device according to claim 9, it has the dot structure of independent light-emitting mode, wherein, organic electroluminescence device comprises the electroluminescence layer as sub-pixel, one or more sub-pixels form pattern in mode arranged side by side simultaneously, and described one or more sub-pixels contain one or more compounds that are selected from aromatic amine compound and styryl aromatic amine compound.
16. electroluminescent device according to claim 9, it includes organic compounds or organometallic compound in electroluminescence layer, and described compound has the electroluminescent peak simultaneously in being no more than the wavelength of 560nm.
17. electroluminescent device according to claim 9, wherein except described electroluminescence layer, described organic layer also comprises charge generation layer.
18. electroluminescent device according to claim 9 is wherein placed one or more layers that is selected from chalcogenide layer, metal halide and metal oxide layer on the internal surface of the electrode of one or two in pair of electrodes.
19. electroluminescent device according to claim 9, the mixing zone of wherein placing reductibility doping agent and organic substance on the internal surface of the electrode of one or two in pair of electrodes, the perhaps mixing zone of oxidisability doping agent and organic substance.
20. an organic solar batteries, it comprises each described organic electroluminescent compounds of claim 1 to 6.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20070091104 | 2007-09-07 | ||
| KR1020070091104 | 2007-09-07 | ||
| KR1020070142004 | 2007-12-31 | ||
| KR1020080026187 | 2008-03-21 |
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| Publication Number | Publication Date |
|---|---|
| CN101468973A true CN101468973A (en) | 2009-07-01 |
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ID=40826810
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311405A (en) * | 2010-07-07 | 2012-01-11 | 三星移动显示器株式会社 | Organic materials and the organic light-emitting device that comprises this organic materials |
| CN105503736A (en) * | 2015-12-08 | 2016-04-20 | 华南理工大学 | N-type compound containing naphthyl[1,2]imidazole as well as preparation and application thereof |
| CN105601570A (en) * | 2016-03-02 | 2016-05-25 | 吉林奥来德光电材料股份有限公司 | Compound containing heterocyclic ligand and preparation method and application thereof |
| CN106795166A (en) * | 2014-10-17 | 2017-05-31 | 罗门哈斯电子材料韩国有限公司 | Various host materials and the organic electroluminescence device comprising the host material |
| CN107075362A (en) * | 2014-11-06 | 2017-08-18 | 罗门哈斯电子材料韩国有限公司 | Organic electroluminescent compounds and the organic electroluminescence device for including the compound |
| CN110790793A (en) * | 2014-07-22 | 2020-02-14 | 环球展览公司 | Organic electroluminescent material and device |
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2008
- 2008-09-08 CN CNA200810178516XA patent/CN101468973A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311405A (en) * | 2010-07-07 | 2012-01-11 | 三星移动显示器株式会社 | Organic materials and the organic light-emitting device that comprises this organic materials |
| CN110790793A (en) * | 2014-07-22 | 2020-02-14 | 环球展览公司 | Organic electroluminescent material and device |
| CN106795166A (en) * | 2014-10-17 | 2017-05-31 | 罗门哈斯电子材料韩国有限公司 | Various host materials and the organic electroluminescence device comprising the host material |
| CN107075362A (en) * | 2014-11-06 | 2017-08-18 | 罗门哈斯电子材料韩国有限公司 | Organic electroluminescent compounds and the organic electroluminescence device for including the compound |
| CN107075362B (en) * | 2014-11-06 | 2019-10-11 | 罗门哈斯电子材料韩国有限公司 | Organic electroluminescent compounds and organic electroluminescence device comprising the compound |
| CN105503736A (en) * | 2015-12-08 | 2016-04-20 | 华南理工大学 | N-type compound containing naphthyl[1,2]imidazole as well as preparation and application thereof |
| CN105601570A (en) * | 2016-03-02 | 2016-05-25 | 吉林奥来德光电材料股份有限公司 | Compound containing heterocyclic ligand and preparation method and application thereof |
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