CN108137633A - Metal organic complex, high polymer, mixture, composition and organic electronic device - Google Patents

Metal organic complex, high polymer, mixture, composition and organic electronic device Download PDF

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CN108137633A
CN108137633A CN201680059799.9A CN201680059799A CN108137633A CN 108137633 A CN108137633 A CN 108137633A CN 201680059799 A CN201680059799 A CN 201680059799A CN 108137633 A CN108137633 A CN 108137633A
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organic
atoms
alkane
metal organic
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施超
潘君友
闫晓林
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Guangzhou Chinaray Optoelectronic Materials Ltd
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/22—Luminous paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials

Abstract

The invention discloses a kind of metal organic complexes, include its high polymer, mixture, composition and organic electronic device.Ortho position substitution ylidene ligands are included in this metal organic complex, since this kind of ligand includes certain steric hindrance ortho-substituent, so that entire metal organic complex has good rigidity, chemistry and thermal stability, relatively narrow luminescent spectrum and preferable excitation purity can be obtained, and stability and luminous efficiency also get a promotion.

Description

Metal organic complex, high polymer, mixture, composition and organic electronic device Technical field
The present invention relates to novel organic photoelectrical material field more particularly to a kind of metal organic complexes, include its high polymer, mixture, composition and organic electronic device.
Background technique
Due to optics and electric property that organic semiconducting materials have diversity, manufacturing cost relatively low and excellent in synthesis, Organic Light Emitting Diode (OLED) has very big potentiality in the application aspect of photoelectric device (such as flat-panel monitor and illumination).
In order to improve the luminous efficiency of Organic Light Emitting Diode, the various luminescent material systems based on fluorescence and phosphorescence are developed, has the characteristics that high reliablity using the Organic Light Emitting Diode of fluorescent material, but its its internal electroluminescence quantum efficiency under electric field excitation is restricted to 25%, this is because it is 1: 3 that exciton, which generates singlet excited and the likelihood ratio of triplet excited state,.1999, three (2- phenylpyridines) were closed iridium Ir (ppy) by the Thomson professor of University of Southern California, the U.S. and professor Forrest of Princeton University3It is doped to N, in bis- carbazole biphenyl of N- (CBP), is successfully prepared green electro phosphorescent device, this causes people to the great interest of complex phosphorescence material.Due to the introducing of heavy metal, molecular spin orbit coupling is improved, phosphorescent lifetime is shortened, enhanced the intersystem crossing of molecule, phosphorescence is enable smoothly to emit.And this kind of complex reaction is mildly, it may be convenient to change complex structure and substituent group, adjust launch wavelength, obtain the electromechanical phosphorescent material of function admirable.So far, the internal quantum of phosphorescent OLED has been approached 100%.However, most of phosphor material luminescent spectrums are wide, excitation purity is poor, it is unfavorable for high-end display.
Summary of the invention
Based on this, it is necessary to provide that a kind of luminescent spectrum is relatively narrow and the preferable metal organic complex of excitation purity, include its high polymer, mixture, composition and organic electronic device.
A kind of metal organic complex has following general formula (1):
Wherein, Ar1Or Ar2Selected from aromatic hydrocarbon, heteroaryl perfume (or spice) cyclic hydrocarbon, by R1Substituted aromatic hydrocarbon or by R1Substituted heteroaryl perfume (or spice) cyclic hydrocarbon；
Ar3Selected from heteroaryl perfume (or spice) cyclic hydrocarbon or by R1Substituted heteroaryl perfume (or spice) cyclic hydrocarbon, and Ar3In contain at least one hetero atom N；
R1Selected from H, F, Cl, Br, I, D, CN, NO2、CF3、B(OR2)2、Si(R2)3, linear paraffin, alkane ether, the alkane thioether containing 1~10 carbon atom, the branched paraffin containing 1~10 carbon atom, the cycloalkane containing 1~10 carbon atom, the alkane ether containing 3~10 carbon atoms or the alkane sulfide group containing 3~10 carbon atoms, R1In active site can be by R2Replace, R1In non-adjacent methylene (CH2) It can be by R2C=CR2, C=C, Si (R2)2、Ge(R2)2、Sn(R2)2, C=O, C=S, C=Se, C=N (R2), O, S ,-COO- or CONR2Replacement, R1In H can be by D, F, Cl, Br, I, CN, N2, include R2Aromatic amine, the aromatic amine comprising aromatic group, the aromatic amine comprising miscellaneous aromatic rings, carbazole or substituted carbazole replacement；
R2For H, D, containing 1~10 fat of carbon atom race alkane, aromatic hydrocarbon, the aromatic rings containing 5~10 annular atoms, the miscellaneous aromatic group containing 5~10 annular atoms, the substituted aromatic rings containing 5~10 annular atoms or the substituted miscellaneous aromatic group containing 5~10 annular atoms；
For two tooth ligands；
M is transition metal element；
M is 0,1 or 2；
N is 1,2 or 3.
A kind of high polymer contains above-mentioned metal organic complex in the repetitive unit of the high polymer.
A kind of mixture, including above-mentioned metal organic complex or above-mentioned high polymer；
The mixture further includes organic functional material.
A kind of composition, including above-mentioned metal organic complex, above-mentioned high polymer or above-mentioned mixture；
The composition further includes organic solvent.
A kind of organic electronic device, including above-mentioned metal organic complex or above-mentioned high polymer.
It include ortho position substitution ylidene ligands in this metal organic complex, since this kind of ligand includes certain steric hindrance ortho-substituent, so that entire metal organic complex has good rigidity, chemistry and thermal stability, relatively narrow luminescent spectrum and preferable excitation purity can be obtained, and stability and luminous efficiency also get a promotion.
Detailed description of the invention
Fig. 1 is the normalized luminescent spectrum figure of metal organic complex Ir-1~Ir-5 made from embodiment 2~6.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, specific embodiments of the present invention will be described in detail in the following with reference to the drawings and specific embodiments.In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention.But the invention can be embodied in many other ways as described herein, those skilled in the art can make similar improvements without departing from the spirit of the invention, therefore the present invention is not limited to the specific embodiments disclosed below.
In the present invention, composition and printing ink or ink have the same meaning, and can be interchanged between them.
In the present invention, material of main part, host material, Host or Matrix material have the same meaning, and can be interchanged between them.
In the present invention, metallo-organic complex, metal organic complex, metal organic complex have the same meaning, and can be interchanged.
The present invention relates to one kind to have logical formula (I) metal organic complex as follows:
Wherein, Ar1Or Ar2Selected from aromatic hydrocarbon, heteroaryl perfume (or spice) cyclic hydrocarbon, by R1Substituted aromatic hydrocarbon or by R1Substituted heteroaryl perfume (or spice) cyclic hydrocarbon；
Ar3Selected from heteroaryl perfume (or spice) cyclic hydrocarbon or by R1Substituted heteroaryl perfume (or spice) cyclic hydrocarbon, and Ar3In contain at least one hetero atom N；
R1Selected from H, F, Cl, Br, I, D, CN, NO2、CF3、B(OR2)2、Si(R2)3, linear paraffin, alkane ether, the alkane thioether containing 1~10 carbon atom, the branched paraffin containing 1~10 carbon atom, the cycloalkane containing 1~10 carbon atom, the alkane ether containing 3~10 carbon atoms or the alkane sulfide group containing 3~10 carbon atoms, R1In active site can be by R2Replace, R1In non-adjacent methylene (CH2) can be by R2C=CR2, C=C, Si (R2)2、Ge(R2)2、Sn(R2)2, C=O, C=S, C=Se, C=N (R2), O, S ,-COO- or CONR2Replacement, R1In H can be by D, F, Cl, Br, I, CN, N2, include R2Aromatic amine, the aromatic amine comprising aromatic group, the aromatic amine comprising miscellaneous aromatic rings, carbazole or substituted carbazole replacement；
R2For H, D, containing 1~10 fat of carbon atom race alkane, aromatic hydrocarbon, the aromatic rings containing 5~10 annular atoms, the miscellaneous aromatic group containing 5~10 annular atoms, the substituted aromatic rings containing 5~10 annular atoms or the substituted miscellaneous aromatic group containing 5~10 annular atoms；
For two tooth ligands；
M is transition metal element；
M is 0,1 or 2；
N is 1,2 or 3.
Preferably, Ar1Or Ar2Selected from the aromatic ring with 5~22 annular atoms, by R1The aromatic ring with 5~22 annular atoms that replaces, the heteroaromatic rings with 5~22 annular atoms or by R1The heteroaromatic rings with 5~22 annular atoms replaced.
It is furthermore preferred that Ar1Or Ar2Selected from the aromatic ring with 5~18 annular atoms, by R1The aromatic ring with 5~18 annular atoms that replaces, the heteroaromatic rings with 5~18 annular atoms or by R1The heteroaromatic rings with 5~18 annular atoms replaced.
Most preferably, Ar1Or Ar2Selected from the aromatic ring with 5~12 annular atoms, by R1The aromatic ring with 5~12 annular atoms that replaces, the heteroaromatic rings with 5~12 annular atoms or by R1The heteroaromatic rings with 5~12 annular atoms replaced.
Preferably, Ar3Selected from the heteroaromatic rings with 5~22 annular atoms or by R1The heteroaromatic rings with 5~22 annular atoms replaced, Ar3In contain at least one ring hetero atom N.
It is furthermore preferred that Ar3Selected from the heteroaromatic rings with 5~18 annular atoms or by R1What is replaced has 5~18 The heteroaromatic rings of a annular atom, Ar3In contain at least one ring hetero atom N.
Preferably, Ar3Selected from the heteroaromatic rings with 5~12 annular atoms or by R1The heteroaromatic rings with 5~12 annular atoms replaced, Ar3In contain at least one ring hetero atom N.
Aromatic group refers to the alkyl for containing at least one aromatic ring, including monocyclic groups and polycyclic loop system.Heteroaromatic group refers to the alkyl (containing hetero atom) comprising at least one hetero-aromatic ring, including monocyclic groups and polycyclic loop system.These polycyclic rings can have two or more rings, and two of them carbon atom is shared by two adjacent rings, i.e. condensed ring.These polycyclic ring species, at least one is aromatics or heteroaromatic.For the purpose of the present invention, aromatic series or heteroaromatic ring system not only include the system of aromatic radical or heteroaryl perfume base, and, plurality of aryl or heteroaryl can also be interrupted (the non-H atom of < 10% by short non-aromatic unit, preferably smaller than 5% non-H atom, such as C, N or O atom)., 9 '-spiral shell, two fluorenes, 9,9- diaryl fluorenes, triaryl amine, the systems such as diaryl ether, for the goal of the invention it also hold that being aromatic ring system.
Specifically, the example of aromatic group has: benzene, naphthalene, anthracene, phenanthrene, perylene, aphthacene, pyrene, BaP, triphenylene, acenaphthene, fluorenes and its derivative.
Specifically, the example of heteroaromatic group has: furans, benzofuran, thiophene, benzothiophene, pyrroles, pyrazoles, triazole, imidazoles, oxazole, oxadiazoles, thiazole, tetrazolium, indoles, carbazole, pyrrolo- imidazoles, pyrrolopyrrole, Thienopyrroles, thienothiophene, furans and pyrroles, furans and furans, thienofuran, benzo isoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinolin, cinnoline, quinoxaline, phenanthridines, primary pyridine, quinazoline, quinazolinone and its derivative.
In a preferred embodiment, Ar1、Ar2Or Ar3It can be selected from one in the group with following general formula:
Wherein, X1For CR1Or N, and for Ar3, at least one X1For N；
Y1For CR2R3、SiR2R3、NR2, C (=O), S or O；
R1、R2Or R3Selected from H, D, straight chained alkyl with 1~20 C atom, alkoxy with 1~20 C atom, thio alkoxy group with 1~20 C atom, branched alkyl with 3~20 C atoms, cricoid alkyl with 3~20 C atoms, alkoxy with 3~20 C atoms, thio alkoxy group with 3~20 C atoms, silyl-group with 3~20 C atoms, substituted keto group with 1~20 C atom, alkoxycarbonyl groups with 2~20 C atoms, aryloxycarbonyl group with 7~20 C atoms, cyano group (- CN), carbamoyl group (- C (=O) NH2), halogen formyl group (- C (=O)-X, wherein X represents halogen atom), formyl group (- C (=O)-H), isocyano group group, isocyanate groups, thiocyanates group, isothiocyanates group, hydroxyl group, nitryl group, CF3One of group, Cl, Br, F, crosslinkable group, the substituted or unsubstituted aromatics with 5~40 annular atoms, the substituted or unsubstituted heteroaromatic ring system with 5~40 annular atoms, the aryloxy group with 5~40 annular atoms and heteroaryloxy group with 5~40 annular atoms or more than one combination, wherein, one or more group R1、R2、R3Can each other and/or with it is above-mentioned Group bonding forms monocycle or polycyclic aliphatic series or aromatics ring system.
Preferably, R1、R2Or R3Selected from H, D, straight chained alkyl with 1~10 C atom, alkoxy with 1~10 C atom, thio alkoxy group with 1~10 C atom, branch or cricoid alkyl with 3~10 C atoms, branch or cricoid alkoxy with 3~10 C atoms, branch or cricoid thio alkoxy group with 3~10 C atoms, branch or cricoid silyl-group with 3~10 C atoms, substituted keto group with 1 to 10 C atom, alkoxycarbonyl groups with 2 to 10 C atoms, aryloxycarbonyl group with 7~10 C atoms, cyano group (- CN), carbamoyl group (- C (=O) NH2), halogen formyl group (- C (=O)-X, wherein X represents halogen atom), formyl group (- C (=O)-H), isocyano group group, isocyanate groups, thiocyanates group, isothiocyanates group, hydroxyl group, nitryl group, CF3One of group, Cl, Br, F, crosslinkable group, the substituted or unsubstituted aromatics ring system with 5~20 annular atoms, the substituted or unsubstituted heteroaromatic ring system with 5~20 annular atoms, the aryloxy group with 5~20 annular atoms and heteroaryloxy group with 5~20 annular atoms or at least one combination, wherein, one or more group R1、R2、R3Monocycle or polycyclic aliphatic series or aromatics ring system can be formed each other and/or with above-mentioned group bonding.
Preferably, Ar1Or Ar2One of the substituent group formed is further substituted selected from following building stone or following building stone:
Preferably, Ar3One of the substituent group formed is further substituted selected from following building stone or following building stone:
Preferably, metal organic complex disclosed by the invention is selected from one of the compound with following general formula:
Wherein, R3 is selected from-H ,-F ,-Cl, Br, I ,-D ,-CN ,-NO2、-CF3、B(OR2)2、Si(R2)3, linear paraffin, alkane ether, the alkane thioether containing 1~10 carbon atom, the branched paraffin containing 1~10 carbon atom, the cycloalkane containing 1~10 carbon atom, the alkane ether containing 3~10 carbon atoms, the alkane sulfide group hydrogen containing 3~10 carbon atoms or the aryl containing 6~10 carbon atoms；
R4 is selected from-H ,-F ,-Cl, Br, I ,-D ,-CN ,-NO2、-CF3、B(OR2)2、Si(R2)3, linear paraffin, alkane ether, the alkane thioether containing 1~10 carbon atom, the branched paraffin containing 1~10 carbon atom, the cycloalkane containing 1~10 carbon atom, the alkane ether containing 3~10 carbon atoms, the alkane sulfide group hydrogen containing 3~10 carbon atoms or the aryl containing 6~10 carbon atoms；
X is 0,1 or 2；
Y is 0,1,2 or 3；
Z is 0,1,2,3 or 4；
U is 0,1,2,3,4 or 5；
V is 0,1,2,3,4,5 or 6.
Preferably, Ar1For aromatic rings or miscellaneous aromatic rings, Ar1It is a kind of in the compound with following general formula C1~C10:
Wherein, R5~R59Selected from-H ,-F ,-Cl, Br, I ,-D ,-CN ,-NO2、-CF3、B(OR2)2、Si(R2)3, linear paraffin, alkane ether, the alkane thioether containing 1~10 carbon atom, containing 1~10 carbon atom Branched paraffin, the cycloalkane containing 1~10 carbon atom, the alkane ether containing 3~10 carbon atoms, the alkane sulfide group hydrogen containing 3~10 carbon atoms or the aryl containing 6~10 carbon atoms；
Dotted line expression is attached in the form of singly-bound.
Preferably,For single anion ligand,Selected from one of the compound with following general formula L1~L15:
Wherein, R60~R129Selected from-H ,-F ,-Cl, Br, I ,-D ,-CN ,-NO2、-CF3、B(OR2)2、Si(R2)3, linear paraffin, alkane ether, the alkane thioether containing 1~10 carbon atom, the branched paraffin containing 1~10 carbon atom, the cycloalkane containing 1~10 carbon atom, the alkane ether containing 3~10 carbon atoms, the alkane sulfide group hydrogen containing 3~10 carbon atoms or the aryl containing 6~10 carbon atoms；
Dotted line indicates the key being connected directly with M.
M is transition metal element.
In a preferred embodiment, M is selected from chromium (Cr), molybdenum (Mo), tungsten (W), ruthenium (Ru), rhodium (Rh), nickel (Ni), silver-colored (Ag), copper (Cu), zinc (Zn), palladium (Pd), golden (Au), starves (Os), rhenium (Re), iridium (Ir) or platinum (Pt).
In a particularly preferred embodiment, M is Ir or Pt.
From the point of view of heavy atoms effect, Ir or Pt is preferably used as to the central metal M of above-mentioned metal organic complex.Iridium is most preferred, this is because iridium is chemically stable, and there is significant heavy atoms effect can obtain height Luminous efficiency.
The specific example of suitable metal organic complex disclosed by the invention is given below, comprising:
Preferably, metal organic complex disclosed by the invention is luminescent material, the emission wavelength of metal organic complex 300 between 1000nm, preferably 350 between 900nm, preferably 400 between 800nm.What is herein referred to luminous refers to luminescence generated by light or electroluminescent.
Preferably, photoluminescence efficiency >=30% of metal organic complex disclosed by the invention, more excellent is >=40%, and more excellent is >=50%, and optimal is >=60%.
Preferably, metal organic complex disclosed by the invention is also possible to not luminescent material.
The invention further relates to a kind of high polymer, at least one repetitive unit includes just like structure shown in general formula (I) in high polymer.
Preferably, high polymer is non-conjugated highpolymer, wherein the structural unit as shown in logical formula (I) is on side chain.
Preferably, high polymer is conjugated highpolymer.
The invention further relates to a kind of mixtures, including metal organic complex disclosed by the invention or high polymer disclosed by the invention and organic functional material.
Organic functional material includes hole (also referred to as electric hole) injection or transmission material (HIM/HTM), hole barrier materials (HBM), electron injection or transmission material (EIM/ETM), electron-blocking materials (EBM), organic host materials (Host), singlet emitters (fluorescent illuminant), hot activation delayed fluorescence luminescent material (TADF), triplet emitters (phosphorescent emitter), especially luminescent metal organic coordination compound and organic dyestuff.Such as various organic functional materials are described later in detail in WO2010135519A1, US20090134784A1 and WO 2011110277A1, the full content in this 3 patent document is incorporated herein by reference hereby.
Organic functional material can be small molecule or high polymer material.
It is not polymer, oligomer, the molecule of dendritic or blend that term " small molecule " as defined herein, which refers to,.In particular, there is no repetitive structure in small molecule.Molecular weight≤3000 gram/mol of small molecule, preferably≤2000 gram/mol, preferably≤1500 gram/mol.
High polymer, i.e. Polymer include homopolymer (homopolymer), copolymer (copolymer), block copolymer (block copolymer).In addition in the present invention, high polymer also includes tree (dendrimer), Synthesis and application in relation to tree refer to [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH&Co.KGaA, 2002, Ed.George R.Newkome, Charles N.Moorefield, Fritz Vogtle.].
Conjugated highpolymer (conjugated polymer) is a kind of high polymer, its main chain (backbone) is mainly the sp by C atom2Hybridized orbit is constituted, and famous example has: polyacetylene polyacetylene and poly (phenylene vinylene), and the C atom on main chain can also be replaced by other non-C atoms, and as the sp on main chain2When hydridization is interrupted by some natural defects, it is still considered as being conjugated highpolymer.In addition in the present invention conjugated highpolymer also include include arylamine (aryl amine), aryl hydrogen phosphide (aryl phosphine) and other heterocyclic arenes (heteroarmotics), metallo-organic complex (organometallic complexes) etc. on main chain.
Preferably, in mixture disclosed by the invention, the content of metal organic complex is 0.01 to 30wt%, preferably 0.1 to 20wt%, preferably 0.2 to 15wt%, most preferably 2 to 15wt%.
Preferably, mixture disclosed by the invention includes metal organic complex disclosed by the invention or high polymer disclosed by the invention and triplet host material.
Preferably, mixture disclosed by the invention includes metal organic complex disclosed by the invention or high polymer disclosed by the invention and triplet host material and triplet emitters.
Preferably, mixture disclosed by the invention includes metal organic complex disclosed by the invention or high polymer disclosed by the invention and hot activation delayed fluorescence luminescent material (TADF).
Some more detailed descriptions (but not limited to this) are made to triplet host material, triplet emitters and TADF material below.
1, triplet host material (Triplet Host):
The example of triplet host material is not particularly limited, and any metal complex or organic compound may all be used as matrix, as long as its triplet energy ratio illuminator, especially triplet emitters or phosphorescent emitter are higher.
It can be used as the example of the metal complex of triplet matrix (Host) including (but not limited to) following general structure:
Wherein, M is a metal；(y3-y4) it is one liang of tooth ligand, Y3And Y4Independently selected from C, N, O, P and S；L is an assistant ligand；M is an integer, value from 1 to this metal maximum coordination number；M+n is the maximum coordination number of this metal.
In a preferred embodiment, the metal complex that can be used as triplet matrix has following form:
Wherein, (O-N) is one liang of tooth ligand, wherein metal and O and N Atomic coordinate.
In some embodiment, M is optional in Ir and Pt.
Can be used as the organic compound of triplet main body example be selected from include aromatic hydrocarbon ring base compound, Such as benzene, biphenyl, triphenyl, benzo, fluorenes；It include the compound of fragrant heterocyclic radical, such as dibenzothiophenes, dibenzofurans, dibenzo selenophen, furans, thiophene, benzofuran, benzothiophene, benzo selenophen, carbazole, indole carbazole, pyridine indoles, two pyridine of pyrroles, pyrazoles, imidazoles, triazole type, oxazole, thiazole, oxadiazoles, dislike triazole, dioxazole, thiadiazoles, pyridine, pyridazine, pyrimidine, pyrazine, triazines, oxazines, dislike thiazine, oxadiazines, indoles, benzimidazole, indazole, oxazole, dibenzo oxazole, benzisoxazole, benzothiazole, quinoline, isoquinolin, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, azophenlyene, phenthazine, phenoxazine, benzofuran pyridine, furopyridine, benzothiophene pyridine, thiophene pyridine, two pyridine of benzo selenophen pyridine and selenophen benzo；It include the group of 2 to 10 ring structures, they can be the aromatic hydrocarbon ring group or aromatic heterocycle group of identical or different type, and link together directly with one another or by least one group below, such as oxygen atom, nitrogen-atoms, sulphur atom, silicon atom, phosphorus atoms, boron atom, chain structural unit and aliphatic cyclic group.Wherein, each Ar can be further substituted, and substituent group is chosen as hydrogen, alkyl, alkoxy, amino, alkene, alkynes, aralkyl, miscellaneous alkyl, aryl and heteroaryl.
In a preferred embodiment, triplet host material is optional in the compound comprising at least one following group:
Wherein, R1~R7It can select independently of each other in following group: hydrogen, alkyl, alkoxy, amino, alkene, Alkynes, aralkyl, miscellaneous alkyl, aryl and heteroaryl, when they are aryl or heteroaryl, they and above-mentioned Ar1And Ar2Meaning is identical；N is an integer from 0 to 20；X1~X8It selects in CH or N；X9It selects in CR1R2Or NR1。
R1, R2With the R in the part ETM1It defines identical.
The example of suitable triplet host material is listed in following table:
2, triplet emitters (Triplet Emitter)
Triplet emitters are also referred to as phosphorescent emitter.In a preferred embodiment, triplet emitters are the metal complexes for having formula M (L) n, and wherein M is a metallic atom, be can be when L occurs every time identical or different, it is an organic ligand, it is bonded by one or more positions or coordination is connected on metallic atom M, and n is an integer greater than 1, and preferably selecting is 1,2,3,4,5 or 6.Optionally, these metal complexes are connected on a polymer by one or more positions, preferably by organic ligand.
In a preferred embodiment, metallic atom M choosing preferentially selects Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag, especially preferentially selection Os, Ir, Ru, Rh, Re, Pd or Pt in transition metal element or lanthanide series or actinides.
Preferably, triplet emitters include cheland, i.e. ligand, are coordinated by least two binding sites and metal, and what is given special priority for be triplet emitters includes two or three identical or different bidentates or multidentate ligand.Cheland is conducive to improve the stability of metal complex.
The example of organic ligand can be selected from phenylpyridine derivative, 7,8- benzoquinoline derivatives, 2 (2- thienyl) pyridine derivates, 2 (1- naphthalene) pyridine derivates or 2 phenylchinoline derivatives.All these organic ligands may be all substituted, such as be replaced by fluorine-containing or trifluoromethyl.Assistant ligand can be preferably selected from acetic acid acetone or picric acid.
In a preferred embodiment, the metal complex that can be used as triplet emitters has following form:
Wherein M is a metal, is selected in transition metal element or lanthanide series or actinides；
It can be identical or different when Ar1 occurs every time, be a cyclic group, wherein at least include a donor atom, that is, have the atom of a lone pair electrons, such as nitrogen or phosphorus, pass through its cyclic group and metal coordination connects；It can be identical or different when Ar2 occurs every time, be a cyclic group, wherein at least include a C atom, connect by its cyclic group with metal；Ar1 and Ar2 are linked together by covalent bond, can respectively be taken The one or more substituent groups of band, they can also be linked together by substituent group again；It can be identical or different when L occurs every time, be an assistant ligand, be preferable over double-tooth chelate ligand, preferably monoanionic, bidentate cheland；M is 1,2 or 3, preferably 2 or 3, particularly preferably 3；N is 0,1 or 2, preferably 0 or 1, particularly preferably 0.
The example that the material of some triplet emitters is extremely applied can be found in following patent documents and document: WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 2005033244, WO 2005019373, US 2005/0258742, WO 2009146770, WO 2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO 2010099 20070087219 A1 of 852, WO 2010102709, US, US 20090061681 A1, US 20010053462 A1, Baldo, Thompson et al.Nature 403, (2000), 750-753, US 20090061681 A1, US 20090061681 A1, Adachi et al.Appl.Phys.Lett.78 (2001), 1622-1624, J.Kido et al.Appl.Phys.Lett.65 (1994), 2124, Kido et al.C Hem.Lett.657,1990, US 2007/0252517 A1, Johnson et a1., JACS105,1983,1795, Wrighton, 96,1974,998, Ma et al. of JACS, Synth.Metals 94,1998,245, US 6824895,20010053462 A1 of US 7029766, US 6835469, US 6830828, US, WO 2007095118 A1, US 2012004407A1, WO 2012007088A1, WO2012007087A1 , WO 2012007086A1, US 2008027220A1, WO 2011157339A1, CN 102282150A, WO 2009118087A1.The full content in the above-mentioned patent document and document listed is incorporated herein by reference hereby.
The example of some suitable triplet emitters is listed in following table；
3, hot activation delayed fluorescence luminescent material (TADF):
Traditional organic fluorescence materials can only be shone using 25% singlet exciton to be formed is electrically excited, and the internal quantum efficiency of device is lower (up to 25%).Although phosphor material passes through between being since the strong SO coupling in heavy atom center enhances, it can efficiently use and be electrically excited the singlet exciton to be formed and Triplet exciton, the internal quantum efficiency of device is made to reach 100%.But phosphor material is expensive, and stability of material is poor, and device efficiency the problems such as serious of roll-offing limits its application in OLED.Hot activation delayed fluorescence luminescent material is the third generation luminous organic material developed after organic fluorescence materials and organic phosphorescent material.Such material generally has small singlet-triplet poor (Δ Est), triplet excitons can by it is counter be between pass through be transformed into singlet exciton shine.This can make full use of the singlet exciton and triplet excitons that are electrically excited lower formation.Device Internal quantum efficiency can reach 100%.
Traditional organic fluorescence materials can only be shone using 25% singlet exciton to be formed is electrically excited, and the internal quantum efficiency of device is lower (up to 25%).Although phosphor material passes through between being since the strong SO coupling in heavy atom center enhances, it can efficiently use and be electrically excited the singlet exciton to be formed and Triplet exciton, the internal quantum efficiency of device is made to reach 100%.But phosphor material is expensive, and stability of material is poor, and device efficiency the problems such as serious of roll-offing limits its application in OLED.Hot activation delayed fluorescence luminescent material is the third generation luminous organic material developed after organic fluorescence materials and organic phosphorescent material.Such material generally has small singlet-triplet poor (Δ Est), triplet excitons can by it is counter be between pass through be transformed into singlet exciton shine.This can make full use of the singlet exciton and triplet excitons that are electrically excited lower formation.Device internal quantum efficiency can reach 100%.
The example of some suitable TADF luminescent materials is listed below:
The invention further relates to a kind of composition or printing ink, wherein composition or printing ink include a kind of above-mentioned metal organic complex, above-mentioned high polymer or said mixture and organic solvent.
Preparation that the present invention further provides a kind of from solution includes the film of metal organic complex or high polymer disclosed by the invention.
When for printing technology, the viscosity of ink, surface tension is important parameter.The surface tension parameter of suitable ink is suitable for specific substrate and specific printing process.
In a preferred embodiment, ink disclosed by the invention is in operating temperature or surface tension at 25 DEG C about in 19dyne/cm to 50dyne/cm range；More preferably in 22dyne/cm to 35dyne/cm range；Preferably in 25dyne/cm to 33dyne/cm range.
In another preferred embodiment, viscosity of the ink disclosed by the invention at operating temperature or 25 DEG C About in 1cps to 100cps range；Preferably in 1cps to 50cps range；More preferably in 1.5cps to 20cps range；Preferably in 4.0cps to 20cps range.The composition so prepared will be suitable for ink jet printing.
Viscosity can be adjusted by different methods, as chosen the concentration with functional material in ink by suitable solvent.Disclosed by the invention includes that the ink of described ground metal organic complex or high polymer can facilitate people that will print ink to adjust according to printing process used in range appropriate.Generally, the weight ratio for the functional material that composition disclosed by the invention includes is 0.3%~30wt% range, is preferably 0.5%~20wt% range, is preferably 0.5%~15wt% range, it is more preferably 0.5%~10wt% range, it is best for 1%~5wt% range.
In ink disclosed by the invention, organic solvent is selected from based on aromatics or heteroaromatic solvent, especially aliphatic chain/cyclosubstituted arsol or aromatics ketone solvent or aromatic ether solvents.
More preferably, organic solvent is selected from based on aromatics or heteroaromatic solvent, it include: to diisopropyl benzene, penta benzene, naphthane, cyclohexyl benzene, chloronaphthalene, 1, 4- dimethylnaphthalene, 3- isopropyl biphenyl, p-Methylisopropylbenzene, diamyl benzene, 3 penta benzene, amyl toluene, ortho-xylene, meta-xylene, paraxylene, adjacent diethylbenzene, NSC 62102, p-Diethylbenzene, 1, 2, 3, 4- durene, 1, 2, 3, 5- durene, 1, 2, 4, 5- durene, butylbenzene, detergent alkylate, dihexyl benzene, dibutyl benzene, to diisopropyl benzene, 1- methoxynaphthalene, cyclohexyl benzene, dimethylnaphthalene, 3- isopropyl biphenyl, p-Methylisopropylbenzene, 1- methyl naphthalene, 1, 2, 4- trichloro-benzenes, 1, 3- dipropoxy benzene, 4, 4- difluoro-diphenylmethane, 1, 2- dimethoxy-4 ' (1- acrylic) benzene, diphenyl-methane, 2- phenylpyridine, 3- phenylpyridine, N- methyldiphenylamine, 4- isopropyl biphenyl, α, α-dichloro diphenyl methane, 4- (3- phenyl propyl) pyridine, Ergol, 1, bis- (3, the 4- 3,5-dimethylphenyl) ethane of 1-, 2- isopropyl naphthalene, benzyl ether etc.；Solvent based on ketone: 1-tetralone, 2- tetralone, 2- (phenyl epoxy) tetralone, 6- (methoxyl group) tetralone, acetophenone, propiophenone, benzophenone and their derivative, such as 4- methyl acetophenone, 3- methyl acetophenone, 2- methyl acetophenone, 4- methyl phenyl ketone, 3- methyl phenyl ketone, 2- methyl phenyl ketone, isophorone, 2,6,8- trimethyl -4- nonanone, fenchone, methyl n-heptyl ketone, 3- nonanone, butyl ketone, 2- decanone, 2,5- acetyl butyryl, phorone, two n-pentyl ketone；Aromatic ether solvents: 3- phenoxytoluene, butyl phenyl ether, benzyl butyl benzene, p-anisaldehyde dimethyl-acetal, tetrahydro -2- phenoxy group -2H- pyrans, 1, 2- dimethoxy-4 '-(1- acrylic) benzene, 1, 4- benzdioxan, 1, 3- dipropyl benzene, 2, 5- dimethoxy-p, this ether of 4- ethyl, 1, 2, 4- trimethoxy-benzene, 4- (1- acrylic) -1, 2- dimethoxy benzene, 1, 3- dimethoxy benzene, glycidyl phenyl ether, dibenzyl ether, 4- tert-butyl anisole, trans--anethole, 1, 2- dimethoxy benzene, 1- methoxynaphthalene, diphenyl ether, 2- phenoxy group methyl ether, 2- phenoxy group tetrahydrofuran, ethyl -2- naphthyl ether, amyl ether c hexyl ether, dioctyl ether, butyl cellosolve, diethylene glycol diethyl Ether, diethylene glycol butyl methyl ether, dibutyl ethylene glycol ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether；Ester solvent: sad alkyl ester, decanedioic acid alkyl ester, stearic acid alkyl ester, benzoic acid alkyl esters, phenylacetic acid alkyl ester, cinnamic acid alkyl ester, oxalic acid alkyl ester, maleic acid alkyl ester, alkane lactone, oleic acid alkyl ester etc..
It is furthermore preferred that organic solvent is selected from aliphatic ketone, comprising: methyl n-heptyl ketone, 3- nonanone, butyl ketone, 2- decanone, 2,5- acetyl butyryl, 2,6,8- trimethyl -4- nonanones, phorone, two n-pentyl ketone etc..
More preferably, organic solvent is selected from fatty ether, comprising: amyl ether, hexyl ether, dioctyl ether, butyl cellosolve, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, dibutyl ethylene glycol ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether etc..
Preferably, printing ink also includes another organic solvent.Another organic solvent can be selected from: methanol, ethyl alcohol, 2-methyl cellosolve, methylene chloride, chloroform, chlorobenzene, o-dichlorohenzene, tetrahydrofuran, methyl phenyl ethers anisole, morpholine, toluene, ortho-xylene, meta-xylene, paraxylene, 1,4 dioxanes, acetone, methyl ethyl ketone, 1,2 dichloroethanes, 3- phenoxytoluene, 1,1,1- trichloroethanes, 1,1, one of 2,2- tetrachloroethanes, ethyl acetate, butyl acetate, dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, naphthane, naphthalane and indenes or more than one mixture.
Preferably, composition disclosed by the invention is a solution.
Preferably, composition disclosed by the invention is a suspension.
Purposes the invention further relates to above-mentioned composition as coating or printing ink when preparing organic electronic device, particularly preferably passes through the preparation method of printing or coating.
Wherein, suitable printing or coating technique are including (but not limited to) inkjet printing, spray printing (Nozzle Printing), typographic printing, silk-screen printing, dip-coating, rotary coating, blade coating, roller printing, reverse roller printing, lithographic printing, flexographic printing, rotary printing, spraying, brushing or bat printing, jet printing (Nozzle printing), slit-type squash type coating etc..It is preferred that ink jet printing, the coating of slit-type squash type, jet printing and intaglio printing.Solution or suspension can additionally comprise one or more components such as surface active cpd, and lubricant, wetting agent, dispersing agent, hydrophobing agent, bonding agent etc., for adjusting viscosity, filming performance improves adhesion etc..Related printing technique, and its to the related request in relation to solution, such as solvent and concentration, viscosity etc., details refer to Helmut Kipphan chief editor " print media handbook: technology and production method " (Handbook of Print Media:Technologies and Production Methods), ISBN3-540-67326-1.
Based on above-mentioned metal organic complex, the present invention also provides a kind of metal organic complex as described above or high polymer organic electronic device application.Organic electronic device includes: Organic Light Emitting Diode (OLED), organic photovoltaic battery (OPV), organic light emission battery (OLEEC), organic field-effect tube (OFET), organic light-emitting field effect pipe, organic laser, organic spin electric device, organic sensor and organic phasmon emitting diode (Organic Plasmon Emitting Diode) etc., especially OLED.In the embodiment of the present invention, preferably the metal organic complex is used in the luminescent layer of OLED device.
The invention further relates to a kind of organic electronic devices, include above-mentioned metal organic complex or above-mentioned high polymer.
In general, organic electronic device includes cathode, anode and the functional layer between cathode and anode, wherein functional layer includes above-mentioned metal organic complex or above-mentioned high polymer.
Organic electronic device can be selected from Organic Light Emitting Diode (OLED), organic photovoltaic battery (OPV), organic light emission battery (OLEEC), organic field-effect tube (OFET), organic light-emitting field effect pipe, organic laser, organic spin electric device, organic sensor and organic phasmon emitting diode (Organic Plasmon Emitting Diode).
Preferably, organic electronic device is electroluminescent device, more preferably OLED.Electroluminescent device includes substrate, anode, luminescent layer and cathode.
Substrate can be opaque or transparent.One transparent substrate can be used to manufacture a transparent light emitting component.It see, for example, the Nature such as Bulovic 1996,380, p29 and Gu etc., Appl.Phys.Lett.1996,68, p2606.Substrate can be rigid or elasticity.Substrate can be plastics, metal, semiconductor wafer or glass.Preferably substrate has a smooth surface.Substrate free of surface defects is especially desirable Selection.In a preferred embodiment, substrate is flexible, optional in thin polymer film or plastics, and glass transition temperature Tg is 150 DEG C or more, preferably more than 200 DEG C, more preferably more than 250 DEG C, preferably more than 300 DEG C.The example of suitable flexible base board has poly- (ethylene glycol terephthalate) (PET) and polyethylene glycol (2,6- naphthalene) (PEN).
Anode may include conductive metal, metal oxide or conducting polymer.Anode can be easily injected into hole into hole injection layer (HIL) or hole transmission layer (HTL) or luminescent layer.In one embodiment, the absolute value of the difference of the HOMO energy level or valence-band level of illuminator in the work function and luminescent layer of anode or the p-type semiconductor material as HIL or HTL or electronic barrier layer (EBL) is less than 0.5eV, preferably it is less than 0.3eV, preferably less than 0.2eV.The example of anode material is including but not limited to Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminium-doped zinc oxide (AZO) etc..Other suitable anode materials be it is known, those of ordinary skill in the art are readily able to select use.Any suitable technology deposition can be used in anode material, and a such as suitable physical vaporous deposition includes rf magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam) etc..In certain embodiments, anode is patterning.Patterned ITO electrically-conductive backing plate is commercially available, and can be used to prepare device according to the present invention.
Cathode may include conductive metal or metal oxide.Cathode can be easily injected into electronics to EIL or ETL or directly into luminescent layer.In one embodiment, the absolute value of the difference of the lumo energy or conduction level of illuminator or the n-type semiconductor as electron injecting layer (EIL) or electron transfer layer (ETL) or hole blocking layer (HBL) is less than 0.5eV in the work function and luminescent layer of cathode, preferably it is less than 0.3eV, preferably less than 0.2eV.In principle, the material of all cathodes that can be used as OLED all may be as the cathode material of device of the present invention.The example of cathode material is including but not limited to Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO etc..Any suitable technology deposition can be used in cathode material, and a such as suitable physical vaporous deposition includes rf magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam) etc..
OLED can also include other function layer, such as hole injection layer (HIL), hole transmission layer (HTL), electronic barrier layer (EBL), electron injecting layer (EIL), electron transfer layer (ETL), hole blocking layer (HBL).It is described in front suitable for the material in these functional layers.
In a preferred embodiment, the luminescent layer of electroluminescent device disclosed by the invention includes above-mentioned metal organic complex or above-mentioned high polymer, and luminescent layer is preferably prepared by the method that solution is processed.
The emission wavelength of luminescent device disclosed by the invention 300 between 1000nm, preferably 350 between 900nm, most preferably 400 between 800nm.
The invention further relates to the application of organic electronic device disclosed by the invention in electronic equipment of various, include, but are not limited to, and show equipment, lighting apparatus, light source, sensor etc..
Below in conjunction with preferred embodiment, the present invention is described, but the present invention is not limited to the following examples, it should be understood that, appended claims summarise the scope of the present invention under the guidance of present inventive concept it should be appreciated by one skilled in the art that, to certain change that various embodiments of the present invention are carried out, will all be covered by the spirit and scope of claims of the present invention.
Specific embodiment
Embodiment 1, metal organic complex and its energy-structure
The energy level of metal organic complex Ir-1~Ir-5 can be calculated by quantum, for example using TD-DFT (time-depentent DFT) by Gaussian03W (Gaussian Inc.), specific analogy method can be found in WO2011141110.Semi-empirical approach " Ground State/Hartree-Fock/Default Spin/LanL2MB " (Charge 0/Spin Singlet) Lai Youhua molecular geometry is used first, and then the energy-structure of organic molecule calculates " TD-SCF/DFT/Default Spin/B3PW91/gen geom=connectiVity pseudo=lanl2 " (Charge 0/Spin Singlet) by TD-DFT (time-depentent DFT) method.HOMO and lumo energy are calculated according to following calibration equation, and S1 and T1 are directly used.
HOMO (eV)=((HOMO (Gaussian) × 27.212) -0.9899)/1.1206
LUMO (eV)=((LUMO (Gaussian) × 27.212) -2.0041)/1.385
Wherein HOMO (G) and LUMO (G) is the direct calculated result of Gaussian 03W, unit Hartree.As a result as shown in Table 1:
Table one
Material HOMO[eV] LUMO[eV] T1[eV] S1[eV]
Ir-1 -5.17 -2.36 2.56 2.80
Ir-2 -5.25 -2.29 2.68 2.87
Ir-3 -5.16 -2.28 2.70 2.91
Ir-4 -5.28 -2.33 2.69 2.92
Ir-5 -5.19 -2.69 2.21 2.41
Embodiment 2, metal organic complex Ir-1 synthesis
Synthetic intermediate 1a
2- bromo-iodobenzene (28.2g, 100mmol), 3,5- dimethylphenyl boronic acid (15g, 100mmol), potassium fluoride (28g, 500mmol), four-(triphenylphosphine) palladiums (4g, 3mmol), dioxane 600mL, it reacts for 24 hours for 80 DEG C under a nitrogen, it is cooled to room temperature, water is added into reaction solution, is extracted with dichloromethane, organic phase washing is finally dry with anhydrous magnesium sulfate, concentration, then use ethyl acetate: petroleum ether=1: 5 cross column purification, obtain 1a (18.27g).
Synthetic intermediate 1b
Intermediate 1a (3.7g, 14.2mmol) is placed in a 250mL round bottom single-necked flask, is joined boron ester (5.4g, 21.3mmol), Pd (dppf) Cl2(0.31g, 0.42mmol), potassium acetate (14g, 140mmol), it is dissolved in 100mL dioxane, 120 DEG C are stirred to react 24 hours, it is cooled to room temperature, concentration, adds water, is repeatedly extracted with methylene chloride, merge organic liquor, concentration, then use ethyl acetate: petroleum ether=1: 3 cross column purification, obtain 1b (3.5g).
Synthetic intermediate 1c
Intermediate 1b (3.7g, 14.2mmol), 2- bromopyridine (2g, 12.6mmol), four-(triphenylphosphine) palladium (0.6g, 0.42mmol), potassium carbonate (20g, 142mmol), iodobenzene (4.89g, 24mmol), dioxane (140mL) and water (70mL), back flow reaction for 24 hours, is cooled to room temperature under a nitrogen, add water into reaction solution, it is extracted with dichloromethane, organic phase washing is finally dry with anhydrous magnesium sulfate, concentration, with ethyl acetate: petroleum ether=1: 6 cross column purification, obtain 1c (2.6g).
Synthetic intermediate 1d
Intermediate 1c (1.2g, 4.6mmol) is placed in a dry bottle with two necks, hydrated iridium trichloride (0.7g, 2mmol), vacuum nitrogen gas recycles three times, and 30mL ethylene glycol monoethyl ether and 10mL water is then added Mixed solution, 110 DEG C are stirred to react 24 hours, are cooled to room temperature, filter, are washed with n-hexane, dry, without being further purified, directly react in next step.
Synthesize embodiment 1: synthesis compound Ir-1
Intermediate 1d (0.37g, 0.25mmol) is placed in a dry bottle with two necks, acetylacetone,2,4-pentanedione (0.25mL, 2mmol), Na2CO3(0.22g, 2mmol), vacuum nitrogen gas recycle three times, and 15mL ethylene glycol monoethyl ether is then added, return stirring is stayed overnight, and is cooled to room temperature, is added water, is extracted with dichloromethane, then it dries, is concentrated, obtains Ir-1 (0.12g) with methylene chloride/ethyl alcohol recrystallization.
Embodiment 3, metal organic complex Ir-2 synthesis
Intermediate 1d (0.744g, 0.5mmol) is placed in a dry bottle with two necks, 1c (0.285g, 1.1mmol), silver trifluoroacetate (0.22g, 1mmol), vacuum nitrogen gas recycles three times, 20mL ethylene glycol monoethyl ether is then added, 150 DEG C are stirred to react 24 hours, it is cooled to room temperature, add water, be extracted with dichloromethane, then dries, concentration, with methylene chloride: petroleum ether=1: 3, which cross column purification, obtains Ir-2 (0.29g).
Embodiment 4, metal organic complex Ir-3 synthesis
Intermediate 1d (0.38g, 0.25mmol) is placed in a dry bottle with two necks, 3- methylphenyl iodonium imidazolide salts (0.15g, 0.5mmol), silver oxide (0.18g, 0.77mmol) vacuum nitrogen gas recycles three times, then 15mL 1 is added, 2- dichloroethanes, 100 DEG C are stirred overnight, it is cooled to room temperature, add water, be extracted with dichloromethane, then dries, concentration, is recrystallized to give Ir-3 (0.13g) with the mixed solvent of methylene chloride and petroleum ether.
Embodiment 5, metal organic complex Ir-4 synthesis
Synthetic intermediate 4a
2- phenylpyridine-iridium dichloro bridge (2g, 1.87mmol) is placed in a dry single port bottle, then The mixed solution that 200mL methylene chloride and 10mL methanol is added is dissolved, then silver trifluoromethanesulfonate (1g, 3.92mmol) is added into mixed liquor, then reaction 8 hours is stirred at room temperature, it filters, filtrate is spin-dried for, yellow solid 4a (2.18g) is obtained.
Synthesize compound Ir-4
4a (2.6g is placed in a dry bottle with two necks, 4mmol), 1c (3g, 11.6mmol), vacuum nitrogen gas recycle three times, then 300mL ethyl alcohol is added, it is stirred at reflux reaction 24 hours, is cooled to room temperature, is filtered, it is dry, obtain yellow solid Ir-4 (2.12g).
Embodiment 6, metal organic complex Ir-5 synthesis
Synthetic intermediate 5a
Intermediate 1b (1.54g, 5mmol), 2- chloroquinoline (0.64g, 4mmol), four-(triphenylphosphine) palladiums (0.138g, 0.12mmol), potassium carbonate (2.76g, 20mmol), dioxane (20mL) and water (10mL), back flow reaction for 24 hours, is cooled to room temperature under a nitrogen, add water into reaction solution, it is extracted with dichloromethane, organic phase washing is finally dry with anhydrous magnesium sulfate, concentration, with ethyl acetate: petroleum ether=1: 6 cross column purification, obtain 5a (0.98g).
Synthetic intermediate 5b
Intermediate 5a (1.42g, 4.6mmol) is placed in a dry bottle with two necks, hydrated iridium trichloride (0.7g, 2mmol), vacuum nitrogen gas recycles three times, the mixed solution of 30mL ethylene glycol monoethyl ether and 10 mL water is then added, 110 DEG C are stirred to react 24 hours, it is cooled to room temperature, it filters, is washed with n-hexane, it is dry, without being further purified, directly react in next step.
Synthesize compound Ir-5
Intermediate 5b (0.42g, 0.25mmol) is placed in a dry bottle with two necks, acetylacetone,2,4-pentanedione (0.25mL, 2mmol), Na2CO3Three times, then (0.22g, 2mmol), vacuum nitrogen gas recycle 15mL ethylene glycol monoethyl ether is added, return stirring is overnight, is cooled to room temperature, adds water, is extracted with dichloromethane, and then dries, and is concentrated, obtains Ir-5 (0.18g) with methylene chloride/ethyl alcohol recrystallization.
The photophysical property of embodiment 7, metal organic complex
Luminescent spectrum measurement is carried out to metal organic complex Ir-1~Ir-5 made from embodiment 2~6 in methylene chloride, obtains Fig. 1.
As seen from Figure 1, the spectrum of metal organic complex Ir-1~Ir-5 all presents relatively narrow transmitting, especially Ir-1 and Ir-2 shows as narrower emission spectra.
The preparation and characterization of embodiment 8, OLED device
It is as follows with ITO/NPD (60nm)/15%Ir-1~Ir-5:mCP (45nm)/TPBi (35nm)/LiF (1nm)/Al (150nm)/cathode OLED device preparation step:
A, the cleaning of electro-conductive glass substrate: for the first time in use, can be cleaned with multi-solvents, such as chloroform, ketone, isopropanol are cleaned, and then carry out UV ozone plasma treatment；
B, HTL (60nm), EML (45nm), ETL (35nm): in high vacuum (1 × 10-6Millibar, mbar) in hot evaporation form；
C, cathode: LiF/Al (1nm/150nm) is in high vacuum (1 × 10-6Millibar) in hot evaporation form；
D, encapsulate: device is encapsulated in nitrogen glove box with ultraviolet hardening resin.
Current Voltage brightness (JVL) characteristic of each OLED device is characterized by characterization equipment, while recording important parameter such as efficiency and external quantum efficiency.Through detecting, the maximum external quantum efficiency of OLED1-5 (corresponding metal organic complexes Ir-1 to Ir-5) is respectively 15.1%, 14.2%, 12.4%, 13.6%, 9.3%.
Further optimization, such as the optimization of device architecture, the Combinatorial Optimization of HTM, ETM and material of main part will further improve the performance of device, especially efficiency, driving voltage and service life.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, and but it cannot be understood as limitations on the scope of the patent of the present invention.It should be pointed out that for those of ordinary skill in the art, without departing from the inventive concept of the premise, various modifications and improvements can be made, and these are all within the scope of protection of the present invention.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (20)

  1. A kind of metal organic complex, which is characterized in that there is logical formula (I) as follows:
    Wherein, Ar1Or Ar2Selected from aromatic hydrocarbon, heteroaryl perfume (or spice) cyclic hydrocarbon, by R1Substituted aromatic hydrocarbon or by R1Substituted heteroaryl perfume (or spice) cyclic hydrocarbon；
    Ar3Selected from heteroaryl perfume (or spice) cyclic hydrocarbon or by R1Substituted heteroaryl perfume (or spice) cyclic hydrocarbon, and Ar3In contain at least one hetero atom N；
    R1Selected from H, F, Cl, Br, I, D, CN, NO2、CF3、B(OR2)2、Si(R2)3, linear paraffin, alkane ether, the alkane thioether containing 1~10 carbon atom, the branched paraffin containing 1~10 carbon atom, the cycloalkane containing 1~10 carbon atom, the alkane ether containing 3~10 carbon atoms or the alkane sulfide group containing 3~10 carbon atoms, R1In active site can be by R2Replace, R1In non-adjacent methylene (CH2) can be by R2C=CR2, C=C, Si (R2)2、Ge(R2)2、Sn(R2)2, C=O, C=S, C=Se, C=N (R2), O, S ,-COO- or CONR2Replacement, R1In H can be by D, F, Cl, Br, I, CN, N2, include R2Aromatic amine, the aromatic amine comprising aromatic group, the aromatic amine comprising miscellaneous aromatic rings, carbazole or substituted carbazole replacement；
    R2For H, D, containing 1~10 fat of carbon atom race alkane, aromatic hydrocarbon, the aromatic rings containing 5~10 annular atoms, the miscellaneous aromatic group containing 5~10 annular atoms, the substituted aromatic rings containing 5~10 annular atoms or the substituted miscellaneous aromatic group containing 5~10 annular atoms；
    For two tooth ligands；
    M is transition metal element；
    M is 0,1 or 2；
    N is 1,2 or 3.
  2. Metal organic complex according to claim 1, which is characterized in that Ar1、Ar2Or Ar3One in the group with following general formula:
    Wherein, X1For CR1Or N, and for Ar3, at least one X1For N；
    Y1For CR2R3、SiR2R3、NR2, C (=O), S or O；
    R1、R2Or R3Selected from H, D, the straight chained alkyl with 1~20 C atom, there is 1~20 C The alkoxy of atom, thio alkoxy group with 1~20 C atom, branched alkyl with 3~20 C atoms, cricoid alkyl with 3~20 C atoms, alkoxy with 3~20 C atoms, thio alkoxy group with 3~20 C atoms, silyl-group with 3~20 C atoms, substituted keto group with 1~20 C atom, alkoxycarbonyl groups with 2~20 C atoms, aryloxycarbonyl group with 7~20 C atoms, cyano group, carbamoyl group, halogen formyl group, formyl group, isocyano group group, isocyanate groups, thiocyanates group, isothiocyanates group, hydroxyl group, nitryl group, CF3One of group, Cl, Br, F, crosslinkable group, the substituted or unsubstituted aromatics with 5~40 annular atoms, the substituted or unsubstituted heteroaromatic ring system with 5~40 annular atoms, the aryloxy group with 5~40 annular atoms and heteroaryloxy group with 5~40 annular atoms or more than one combination.
  3. Metal organic complex according to claim 1, which is characterized in that Ar1Or Ar2One of the substituent group formed is further substituted selected from following building stone or following building stone:
  4. Metal organic complex according to claim 1, which is characterized in that Ar3One of the substituent group formed is further substituted selected from following building stone or following building stone:
  5. Metal organic complex according to claim 1, which is characterized in that Ar1For aromatic rings or miscellaneous aromatic rings, Ar1It is a kind of in the compound with following general formula C1~C10:
    Wherein, R5~R59Selected from-H ,-F ,-Cl, Br, I ,-D ,-CN ,-NO2、-CF3、B(OR2)2、Si(R2)3, linear paraffin, alkane ether, the alkane thioether containing 1~10 carbon atom, the branched paraffin containing 1~10 carbon atom, the cycloalkane containing 1~10 carbon atom, the alkane ether containing 3~10 carbon atoms, the alkane sulfide group hydrogen containing 3~10 carbon atoms or the aryl containing 6~10 carbon atoms；
    Dotted line expression is attached in the form of singly-bound.
  6. Metal organic complex according to claim 1, which is characterized in thatFor single anion ligand,Selected from one of the compound with following general formula L1~L15:
    Wherein, R60~R129Selected from-H ,-F ,-Cl, Br, I ,-D ,-CN ,-NO2、-CF3、B(OR2)2、Si(R2)3, linear paraffin, alkane ether, the alkane thioether containing 1~10 carbon atom, the branched paraffin containing 1~10 carbon atom, the cycloalkane containing 1~10 carbon atom, the alkane ether containing 3~10 carbon atoms, the alkane sulfide group hydrogen containing 3~10 carbon atoms or the aryl containing 6~10 carbon atoms；
    Dotted line indicates the key being connected directly with M.
  7. Metal organic complex according to claim 1, which is characterized in that M is selected from chromium, molybdenum, tungsten, ruthenium, rhodium, nickel, silver, copper, zinc, palladium, gold, hungry, rhenium, iridium or platinum.
  8. Metal organic complex according to claim 1, which is characterized in that one in the compound with following general formula of the metal organic complex:
    Wherein, R3 is-H ,-F ,-Cl, Br, I ,-D ,-CN ,-NO2、-CF3、B(OR2)2、Si(R2)3, linear paraffin, alkane ether, the alkane thioether containing 1~10 carbon atom, the branched paraffin containing 1~10 carbon atom, the cycloalkane containing 1~10 carbon atom, the alkane ether containing 3~10 carbon atoms, the alkane sulfide group hydrogen containing 3~10 carbon atoms or the aryl containing 6~10 carbon atoms；
    R4 is-H ,-F ,-Cl, Br, I ,-D ,-CN ,-NO2、-CF3、B(OR2)2、Si(R2)3, linear paraffin, alkane ether, the alkane thioether containing 1~10 carbon atom, the branched paraffin containing 1~10 carbon atom, the cycloalkane containing 1~10 carbon atom, the alkane ether containing 3~10 carbon atoms, the alkane sulfide group hydrogen containing 3~10 carbon atoms or the aryl containing 6~10 carbon atoms；
    X is 0,1 or 2, y 0,1,2 or 3, z 0,1,2,3 or 4, u 0,1,2,3,4 or 5, v 0,1,2,3,4,5 or 6.
  9. Metal organic complex according to claim 1, which is characterized in that one in the compound with following general formula of the metal organic complex:
  10. A kind of high polymer, which is characterized in that contained in the repetitive unit of the high polymer such as metal organic complex according to any one of claims 1 to 9.
  11. High polymer according to claim 10, which is characterized in that the high polymer is non-conjugated high polymer, and the metal organic complex is located on the side chain of the high polymer.
  12. High polymer according to claim 10, which is characterized in that the high polymer is conjugated highpolymer.
  13. A kind of mixture, which is characterized in that including such as metal organic complex according to any one of claims 1 to 9 or the high polymer as described in any one of claim 10~12；
    The mixture further includes organic functional material.
  14. Mixture according to claim 13, it is characterized in that, the organic functional material is selected from least one of hole-injecting material, hole mobile material, electron transport material, electron injection material, electron-blocking materials, hole barrier materials, organic host materials, singlet emitters, hot activation delayed fluorescence luminescent material, triplet emitters, luminescent metal organic coordination compound and organic dyestuff.
  15. A kind of composition, which is characterized in that including such as metal organic complex according to any one of claims 1 to 9, the high polymer as described in any one of claim 10~12 or the mixture as described in any one of claim 13~14；
    The composition further includes organic solvent.
  16. A kind of organic electronic device, which is characterized in that including such as metal organic complex according to any one of claims 1 to 9 or the high polymer as described in any one of claim 10~12.
  17. Organic electronic device according to claim 16, it is characterized in that, the organic electronic device is Organic Light Emitting Diode, organic photovoltaic battery, organic light emission battery, organic field-effect tube, organic light-emitting field effect pipe, organic laser, organic spin electric device, organic sensor or organic phasmon emitting diode.
  18. Organic electronic device according to claim 16, which is characterized in that the organic electronic device Part is electroluminescent device, and the electroluminescent device includes substrate, anode, luminescent layer and cathode.
  19. Organic electronic device according to claim 18, which is characterized in that comprising such as metal organic complex according to any one of claims 1 to 9 or the high polymer as described in any one of claim 10~12 in the luminescent layer.
  20. Organic electronic device according to claim 18, which is characterized in that the electroluminescent device further includes at least one of hole injection layer, hole transmission layer, electronic barrier layer, electron injecting layer, electron transfer layer and hole blocking layer.
CN201680059799.9A 2015-12-04 2016-09-14 Metal organic complex, high polymer, mixture, composition and organic electronic device Pending CN108137633A (en)

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