WO2017097397A1 - Metal complexes - Google Patents
Metal complexes Download PDFInfo
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- WO2017097397A1 WO2017097397A1 PCT/EP2016/001939 EP2016001939W WO2017097397A1 WO 2017097397 A1 WO2017097397 A1 WO 2017097397A1 EP 2016001939 W EP2016001939 W EP 2016001939W WO 2017097397 A1 WO2017097397 A1 WO 2017097397A1
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- 0 **1[Cn]*(***2)C2C(*)=C1* Chemical compound **1[Cn]*(***2)C2C(*)=C1* 0.000 description 10
- CXNIUSPIQKWYAI-UHFFFAOYSA-N CC(C)(c1ccc2)c(cccc3P(c4ccccc4)c4ccccc4)c3Oc1c2P(c1ccccc1)c1ccccc1 Chemical compound CC(C)(c1ccc2)c(cccc3P(c4ccccc4)c4ccccc4)c3Oc1c2P(c1ccccc1)c1ccccc1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 description 1
- WRKSNZPXFATFFN-UHFFFAOYSA-N CC1(C)c(cccc2P(C)(c3ccccc3)c3ccccc3)c2Oc2c1cccc2P(C)(c1ccccc1)c1ccccc1 Chemical compound CC1(C)c(cccc2P(C)(c3ccccc3)c3ccccc3)c2Oc2c1cccc2P(C)(c1ccccc1)c1ccccc1 WRKSNZPXFATFFN-UHFFFAOYSA-N 0.000 description 1
- XWRTWMYCNRLNCB-UHFFFAOYSA-N c(cc1)ccc1Nc1ccccc1-c1ncccc1 Chemical compound c(cc1)ccc1Nc1ccccc1-c1ncccc1 XWRTWMYCNRLNCB-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
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- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
- H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to metal complexes which are suitable for use, in particular as emitters, in organic electroluminescent devices.
- OLEDs organic electroluminescent devices
- organic semiconductors are used as functional materials
- organometallic complexes that show phosphorescence instead of fluorescence.
- organometallic compounds for quantum mechanical reasons, up to four times energy and power efficiency is possible using organometallic compounds as phosphorescence emitters.
- iridium and platinum complexes are used in particular in phosphorescent OLEDs as triplet emitters.
- the object of the present invention is therefore to provide new metal complexes which are suitable as emitters for use in OLEDs.
- the object is to provide emitters which do not require the use of iridium and platinum as metals and which show good properties in terms of efficiency, operating voltage, service life, color coordinates, sublimability and / or solubility.
- the copper chelate complexes described in more detail below achieve this object and are very well suited for use in an organic electroluminescent device.
- the complexes of the invention are thermally stable and have a low molecular weight, which has a positive effect on the sublimability of the compounds both in the purification and in the production of organic electroluminescent devices from the gas phase. These metal complexes and organic electroluminescent devices, which contain these complexes are therefore the subject of the present invention.
- Cu is copper in the oxidation state +1;
- X is a neutral nitrogen atom, NR 3 , O or S;
- R 1 is the same or different H, D, F, Cl, Br, I at each occurrence
- Formula (3) wherein W is the same or different at each occurrence for CR 3 or N, with the proviso that at most two W are N, and the two dashed bonds represents the linkage with the nitrogen atom or the heteroaryl group in the ligand; is identical or different at each occurrence, a straight-chain alkyl group having 1 to 20 carbon atoms or an alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group may each be substituted with one or more R 3 radicals and wherein one or more non-adjacent CH 2 groups may be replaced by Si (R 3 ) 2, C O, NR 3 , O, S or CONR 3 , or an aromatic or heteroaromatic ring system having from 5 to 40 aromatic ring atoms, each of which may be substituted by one or more R 3 radicals; R 3 is the same or different at each
- R 4 is the same or different at each occurrence, H, D, F or an aliphatic, aromatic and / or heteroaromatic organic radical having 1 to 20 carbon atoms, in which also one or more H atoms may be replaced by F; two or more substituents R 4 may also together form a mono- or polycyclic ring system;
- the drawn circle in the five-membered ring means a 6TT electron system as commonly used in organic chemistry.
- the ligand in the structure of the formula (2) coordinates to the copper via an anionic nitrogen atom and the neutral atom X of the heteroaromatic five- or six-membered ring, so that the ligand is a monoanionically coordinating ligand.
- An aryl group for the purposes of this invention contains 6 to 40 carbon atoms;
- a heteroaryl group contains 2 to 40 C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms gives at least 5.
- the heteroatoms are preferably selected from N, O and / or S.
- the heteroaryl group contains 1, 2 or 3 heteroatoms, of which not more than one is selected from O or S.
- aryl group or heteroaryl group either a simpler aromatic Cyclus, ie benzene, or a simple heteroaromatic cycle, for example pyridine, pyrimidine, thiophene, etc., or a fused aryl or heteroaryl group, for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc., understood.
- An aromatic ring system in the sense of this invention contains 6 to 60 carbon atoms in the ring system.
- a heteroaromatic ring system in the sense of this invention contains 1 to 60 C atoms and at least one heteroatom in the ring system, with the proviso that the sum of C atoms and heteroatoms gives at least 5.
- the heteroatoms are preferably selected from N, O and / or S.
- An aromatic or heteroaromatic ring system in the sense of this invention is to be understood as meaning a system which does not necessarily contain only aryl or heteroaryl groups, but in which several aryls are also present - or heteroaryl groups by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as.
- N or O atom or a carbonyl group may be interrupted.
- systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ethers, stilbene, etc. are to be understood as aromatic ring systems in the context of this invention, and also systems in which two or more aryl groups, for example by a linear or cyclic alkyl group or interrupted by a silyl group.
- biphenyl or terphenyl also be understood as an aromatic or heteroaromatic ring system.
- a cyclic alkyl group in the context of this invention is understood as meaning a monocyclic, a bicyclic or a polycyclic group. If several substituents form an aliphatic ring system with one another, the term "aliphatic ring system" for the purposes of the present invention also includes heteroaliphatic ring systems.
- a C 1 -C 40 -alkyl group in which also individual H atoms or CHB groups can be substituted by the abovementioned groups for example the radicals methyl, ethyl, n-propyl, i-propyl, Cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neo-pentyl, cyclopentyl, n-hexyl, s-hexyl, t -hexyl, 2-hexyl, 3-hexyl, neo -hexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-
- alkenyl group are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl,
- alkynyl groups include ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or Octinyl understood.
- a C 1 to C 8 alkoxy group is meant, for example, ethoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy or 2-methylbutoxy.
- aromatic or heteroaromatic ring system having 5-60 aromatic ring atoms, which may be substituted in each case with the abovementioned radicals and which may be linked via any position on the aromatic or heteroaromatic, are understood, for example, groups which are derived from benzene, naphthalene , Anthracene, benzanthracene, phenanthrene, benzophenanthrene, pyrene, chrysene, perylene, fluoranthene, benzfluoranthene, naphthacene, pentacene, benzpyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans ionofluorene, cis- or trans-monobenzoindenofluorene, cis-
- X is a neutral nitrogen atom.
- the structure of formula (2) is therefore preferably a structure of the following forms) (4),
- Preferred embodiments of the formula (4) are therefore the structures of the formulas (4a) to (4h), the structures of the formulas (4d) to (4h) especially and the structure of the formula (4d) being very particularly preferred,
- the two groups R 1 together with the carbon atoms to which they are attached stand for a group of the formula (3).
- X is a neutral nitrogen atom. Particularly preferably, it is a structure of the following formula (6)
- R 1 is preferably identically or differently selected on each occurrence from the group consisting of H, D, F, one straight-chain alkyl group having 1 to 10 C atoms, preferably having 1 to 5 C atoms, or an alkenyl group having 2 to 0 C atoms, preferably having 2 to 5 C atoms, or a branched or cyclic alkyl group having 3 to 10 C.
- -Atomen preferably having 3 to 6 carbon atoms, wherein the alkyl or alkenyl group may be substituted in each case with one or more radicals R 3 , or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably with 6 to 14 aromatic Ring atoms, which may be substituted by one or more radicals R 3 in each case;
- the two radicals R may also together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system.
- the substituent R 2 is selected from the group consisting of a straight-chain alkyl group having 1 to 10 C atoms, preferably having 1 to 5 C atoms, or an alkenyl group having 2 to 10 C atoms, preferably having 2 to 5 C atoms, or a branched or cyclic alkyl group having 3 to 10 C atoms, preferably having 3 to 6 C atoms, where the alkyl or alkenyl group may each be substituted by one or more radicals R 3 , or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 14 aromatic ring atoms, each of which may be substituted by one or more radicals R 3 .
- R 2 particularly preferably represents an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, in particular an aromatic ring system having 6 to 14 aromatic ring atoms, which may be substituted by one or more radicals R 3 .
- suitable aromatic ring systems are selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, fluorene or spirobifluorenyl, which may each be substituted by one or more radicals R 3 .
- R 3 is identical or different at each occurrence selected from the group consisting of H, D, F, Cl, Br, CN, a straight-chain alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 C atoms, or an alkenyl group having 2 to 10 C atoms, preferably having 2 to 5 C atoms, or a branched or cyclic alkyl group having 3 to 10 C atoms, preferably having 3 to 6 C atoms, wherein the alkyl or alkenyl group may each be substituted by one or more radicals R 4 , but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 14 aromatic ring atoms, each by one or more radicals R 4 may be substituted, but is preferably unsubstituted; in this case, two or more adjacent radicals R 3 together form a mono- or polycyclic, aliphatic,
- R 3 is selected from the group consisting of H, F, Cl, Br, CN, a straight-chain alkyl group having 1 to 5 C atoms or a branched or cyclic alkyl group having 3 to 6 C atoms; in this case, two or more adjacent radicals R 3 together form a mono- or polycyclic aliphatic ring system.
- R 1 when the groups R 1 are not together with the carbon atoms to which they are attached, represent a group of the formula (3), in each occurrence identically or differently selected from the group consisting of H, D, F, one straight-chain alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl or alkenyl group in each case be substituted by one or more radicals R 3 can, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each of which may be substituted by one or more radicals R 3 ; while the two radicals R 1 can also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another;
- R 2 is selected from the group consisting of a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, wherein the alkyl or alkenyl group each may be substituted with one or more radicals R 3 , or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may be substituted by one or more radicals R 3 ;
- R 3 is the same or different at each occurrence selected from the group consisting of H, D, F, Cl, Br, CN, a straight-chain alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms or a branched or cyclic alkyl group with 3 to 10 carbon atoms, where the alkyl or alkenyl group may each be substituted by one or more radicals R 4 , or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, in particular having 6 to 14 aromatic ring atoms, each by a or more radicals R 4 may be substituted, but is preferably unsubstituted; Two or more adjacent radicals R 3 may together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system.
- R 1 when the groups R are not together with the carbon atoms to which they are attached, represent a group of the formula (3), the same or different at each occurrence, selected from the group consisting of H, D, F, a straight-chain Alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms or a branched or cyclic alkyl group having 3 to 6 carbon atoms, wherein the alkyl or alkenyl group may be substituted in each case with one or more radicals R 3 , or an aromatic or heteroaromatic ring system having 6 to 14 aromatic ring atoms, each of which may be substituted by one or more radicals R 3 ;
- the two radicals R 1 can also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another.
- R 2 is selected from the group consisting of a straight-chain alkyl group having 1 to 5 C atoms or an alkenyl group having 2 to 5 C atoms or a branched or cyclic alkyl group having 3 to 6 C atoms, wherein the alkyl or alkenyl group respectively may be substituted by one or more radicals R 3 , or an aromatic or heteroaromatic ring system having 6 to 14 aromatic ring atoms, each of which may be substituted by one or more radicals R 3 ;
- R 3 is identical or different at each occurrence selected from the group consisting of H, F, Cl, Br, CN, a straight-chain alkyl group having 1 to 5 carbon atoms or a branched or cyclic alkyl group having 3 to 6 carbon atoms ; in this case, two or more adjacent radicals R 3 together form a mono- or polycyclic aliphatic ring system.
- ligands L 'are mono- or bidentate ligands, with neutral ligands being preferred, as this produces neutral compounds of formula (1).
- Preferred neutral, monodentate ligands L ' are selected from the group consisting of carbon monoxide, nitrogen monoxide, alkyl cyanides, such as.
- alkyl cyanides such as.
- amines such as.
- Trifluorophosphine trimethylphosphine, tricyclohexylphosphine, tri-te / f-butylphosphine, triphenylphosphine, tris (pentafluorophenyl) phosphine, dimethylphenylphosphine, methyldiphenylphosphine, bis (tert-butyl) phenylphosphine, phosphites, such as.
- Trifluorarsine trimethylarsine, tricyclohexylarsine, tri-ferf-butylarsine, triphenylarsine, tris (pentafluorophenyl) -arsine, stibines, such as. Trifluorostibine, trimethylstibine, tricyclohexylstibine, tri-tert-butylstibin, triphenylstibin, tris (pentafluorophenyl) stibine, nitrogen-containing heterocycles, such as. As pyridine, pyridazine, pyrazine, pyrimidine, triazine, and carbenes, in particular Arduengo carbenes.
- Preferred neutral, bidentate ligands L ' are selected from diamines, such as. B. ethylenediamine, ⁇ , ⁇ , ⁇ ', ⁇ ' tetramethylethylenediamine, propylenediamine, ⁇ , ⁇ , ⁇ ', ⁇ ' -Tetramethylpropylendiamin, cis- or trans-diaminocyclohexane, cis- or trans-N, N, N ', N '-Tetramethyldiaminocyclo- hexane, imines, such as. B.
- o-phenanthroline or diphosphines, such as.
- Particularly preferred ligands L ' are mono- and D / phosphines, especially diphosphines.
- the abovementioned preferred embodiments can be combined with one another as desired. In a particularly preferred embodiment of the invention, the abovementioned preferred embodiments apply simultaneously. Examples of suitable compounds of the formula (1) according to the invention are the structures listed in the table below.
- Another object of the present invention is a process for preparing the compounds of the invention by reacting the corresponding free ligand L in protonated or deprotonated form and ligands L 'with suitable copper salts, optionally in the presence of a base.
- the process can also be carried out in two steps, wherein the ligand L is deprotonated in a first step and is reacted in the second step with a suitable copper salt.
- Suitable and preferred copper salts for the preparation of the corresponding copper complexes are Cu mesityl, Cu amides, Cu [N (CH 2) 4] (Cu-pyrrolidine) or [Cu (NC-CH 3) 4] BF 4 .
- the compounds of the invention in high purity, preferably more than 99% (determined by means of 1 H-NMR and / or HPLC).
- formulations of the metal complexes according to the invention are required. These formulations may be, for example, solutions, dispersions or emulsions. It may be preferable to use mixtures of two or more solvents for this purpose. Suitable and preferred
- Solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, hexamethylindane, veratrol, THF, methyl THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) - Fenchone, 1, 2,3,5-tetramethylbenzene, 1, 2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4- Methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, ⁇ -terpineol, benzothiazole, butylbenzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenz
- Yet another object of the present invention is therefore a formulation containing at least one compound of the invention and at least one further compound.
- the further compound may for example be a solvent.
- the further compound can also be a further organic or inorganic compound which is likewise used in the electronic device, for example a matrix material.
- This further compound may also be polymeric.
- the compounds of the invention described above can be used in electronic devices as the active component. Another object of the invention is therefore the use of a compound of the invention in an electronic device.
- Yet another object of the present invention is a electronic device containing at least one compound according to the invention.
- An electronic device is understood to mean a device which contains anode, cathode and at least one layer, this layer containing at least one organic or organometallic compound.
- the electronic device according to the invention thus contains anode, cathode and at least one layer which contains at least one compound according to the invention.
- Preferred electronic devices are selected from the group consisting of organic electroluminescent devices (OLEDs, PLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field quench devices (O-FQDs), light-emitting electrochemical cells (LECs) or organic laser diodes (O- Laser).
- OLEDs organic electroluminescent devices
- O-ICs organic integrated circuits
- O-FETs organic field-effect transistors
- O-TFTs organic thin-film transistors
- O-LETs organic light-emitting transistors
- O-SCs organic solar cells
- organic optical detectors organic photoreceptors
- O-FQDs organic field quench devices
- LOCs light-emitting electrochemical cells
- O- Laser organic laser diodes
- Active components are generally the organic or inorganic materials incorporated between the anode and cathode, for example, charge injection, charge transport or charge blocking materials, but especially emission materials and matrix materials.
- the compounds according to the invention exhibit particularly good properties as emission material in organic electroluminescent devices.
- a preferred embodiment of the invention are therefore organic electroluminescent devices.
- the organic electroluminescent device includes cathode, anode and at least one emitting layer.
- they may also contain further layers, for example one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, charge generation layers and / or organic or inorganic p / n junctions.
- one or more hole transport layers are p-doped, for example with metal oxides, such as M0O3 or WO3 or with (per) fluorinated low-electron aromatics, and / or that one or more electron-transport layers are n-doped.
- interlayers may be introduced between two emitting layers which, for example, have an exciton-blocking function and / or control the charge balance in the electroluminescent device. It should be noted, however, that not necessarily each of these layers must be present.
- the organic electroluminescent device can be any organic electroluminescent device.
- the organic electroluminescent device can be any organic electroluminescent device.
- multiple emission layers may include multiple emissive layers. If multiple emission layers are present, they preferably have a total of several emission maxima between 380 nm and 750 nm, so that overall white emission results, ie. H.
- various emitting compounds are used which can fluoresce or phosphoresce. Particular preference is given to three-layer systems in which the three layers show blue, green and orange or red emission (for the basic structure see, for example, WO 2005/0110 3) or systems which have more than three emitting layers. It may also be a hybrid system wherein one or more layers fluoresce and one or more other layers phosphoresce.
- the organic electroluminescent device can be used as a display or for general lighting purposes.
- the organic electroluminescent device contains the compound according to the invention as an emitting compound in one or more emitting
- the compound of the present invention is used as an emitting compound in an emitting layer, it is preferably used in combination with one or more matrix materials.
- Mixture of the compound of the invention and the matrix material contains between 0.1 and 99 wt .-%, preferably between 1 and 90 wt .-%, particularly preferably between 3 and 40 wt .-%, in particular between 5 and 15 wt .-% of the compound according to the invention based on the total mixture of emitter and matrix material. Accordingly, the mixture contains between 99.9 and 1 wt .-%, preferably between 99 and 10 wt .-%, particularly preferably between 97 and 60 wt .-%, in particular between 95 and 85 wt .-% of the matrix material based on the total mixture Emitter and matrix material.
- the triplet level of the matrix material is higher than the triplet level of the emitter.
- Suitable matrix materials for the metal complexes according to the invention are ketones, phosphine oxides, sulfoxides and sulfones, eg. B.
- WO 2004/013080 WO 2004/093207, WO 2006/005627 or WO 2010/006680, triarylamines, carbazole derivatives, eg. B. CBP (N, N-bis-carbazolylbiphenyl), m-CBP or in WO 2005/039246, US
- WO 2006/17052 Diazasilolderivate, z. B. according to WO 2010/054729, Diazaphospholderivate, z. B. according to WO 2010/054730, triazine derivatives, z. B. according to WO 2010/015306, WO 2007/063754 or WO 2008/056746, zinc complexes, for. B. according to EP 652273 or WO 2009/062578, Dibenzo- furanderivate, z. B. according to WO 2009/148015, or bridged carbazole derivatives, for. B. according to US 2009/0136779, WO 2010/050778, WO
- a plurality of different matrix materials as a mixture, in particular at least one electron-conducting matrix material and at least one hole-conducting matrix material.
- a preferred combination is, for example, the use of an aromatic ketone, a triazine derivative or a phosphine oxide derivative with a triarylamine derivative or a carbazole derivative as a mixed matrix for the metal complex according to the invention.
- Also preferred is the use of a mixture of a charge-transporting matrix material and an electrically inert matrix material, which is not or not significantly involved in charge transport, such. As described in WO 2010/108579.
- the compounds according to the invention can also be used in other functions in the electronic device, for example as hole transport material in a hole injection or transport layer, as charge generation material, as electron blocking material, as hole blocking material or as electron transport material.
- the compounds according to the invention can be used as matrix material for other phosphorescent metal complexes in an emitting layer.
- low work function metals, metal alloys or multilayer structures of various metals are preferable, such as alkaline earth metals, alkali metals, main group metals or lanthanides (eg, Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.).
- alkaline earth metals alkali metals, main group metals or lanthanides (eg, Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.).
- alloys of an alkali or alkaline earth metal and silver for example an alloy of magnesium and silver.
- further metals which have a relatively high work function such as, for example, B. Ag, which then usually combinations of metals, such as Mg / Ag, Ca / Ag or Ba / Ag are used.
- a metallic cathode and the organic semiconductor may also be preferred to introduce between a metallic cathode and the organic semiconductor a thin intermediate layer of a material with a high dielectric constant.
- Suitable examples of these are alkali metal or alkaline earth metal fluorides, but also the corresponding oxides or carbonates (eg LiF, L 12 O, BaF 2, MgO, NaF, CsF, CS 2 CO 3, etc.).
- organic alkali metal complexes for.
- the layer thickness of this layer is preferably between 0.5 and 5 nm.
- high workfunction materials are preferred.
- the anode has a work function greater than 4.5 eV. Vacuum up.
- metals with a high redox potential such as Ag, Pt or Au
- metal / metal oxide electrodes eg Al / Ni / NiOx, Al / PtOx
- at least one of the electrodes must be transparent or partially transparent in order to allow either the irradiation of the organic material (O-SC) or the extraction of light (OLED / PLED, O-LASER).
- Preferred anode materials are conductive mixed metal oxides. Particularly preferred are indium tin oxide (ITO) or indium zinc oxide (IZO). Also preferred are conductive, doped organic materials, in particular conductive doped polymers, for. B.
- a p-doped hole transport material is applied to the anode as a hole injection layer, suitable p-dopants being metal oxides, for example M0O3 or WO3, or (per) fluorinated electron-deficient aromatics.
- suitable dopants are p-HAT-CN (Hexacyano- bexaazatrt 'p enyien) or the compound NPD9 Novaled.
- the device is structured accordingly (depending on the application), contacted and finally hermetically sealed because the life of such devices drastically shortened in the presence of water and / or air.
- an organic electroluminescent device characterized in that one or more layers are coated with a sublimation process.
- the materials become in vacuum sublimation at an initial pressure of usually less than 10 "5 mbar, preferably less than 10 " 6 mbar evaporated. It is also possible that the initial pressure is even lower or even higher, for example less than 10 -7 mbar.
- an organic electroluminescent device characterized in that one or more layers are coated with the OVPD (Organic Vapor Phase Deposition) method or with the aid of a carrier gas sublimation. The materials are applied at a pressure between 10 -5 mbar and 1 bar.
- OVJP Organic Vapor Jet Printing
- the materials are applied directly through a nozzle and thus structured (for example, BMS Arnold et al., Appl. Phys. Lett.
- an organic electroluminescent device characterized in that one or more layers of solution, such. B. by spm ' coating, or with any printing process such.
- spm ' coating or with any printing process such.
- screen printing flexographic printing, offset printing or Nozzle printing, but more preferably LITI (Light Induced Thermal Imaging, thermal transfer printing) or ink-jet printing (inkjet printing) can be produced.
- LITI Light Induced Thermal Imaging, thermal transfer printing
- ink-jet printing ink-jet printing
- solution processing is preferred because of the high molecular weight.
- the organic electroluminescent device may also be fabricated as a hybrid system by exposing one or more layers
- Solution are applied and one or more other layers are evaporated. It is thus possible, for example, to apply an emitting layer containing a metal complex according to the invention and a matrix material from solution and then evaporate a hole blocking layer and / or an electron transport layer in vacuo.
- a hole blocking layer and / or an electron transport layer in vacuo.
- the electronic devices according to the invention are distinguished by one or more of the following surprising advantages over the prior art:
- Organic Elektrolumineszenzvornchtungen containing the compounds of the invention as emitting materials, especially as orange or red emitting compounds, have a high efficiency and lifetime.
- OLEDs organic Electrolumineszenzvornchtungen containing the compounds of the invention as emitting materials, especially as orange or red emitting compounds, have a high efficiency and lifetime.
- the production of efficient OLEDs while avoiding the rare metals iridium and platinum is possible.
- the compounds according to the invention are thermally stable and readily sublimable. They can therefore be purified both by sublimation, as well as process in the production of organic Elektrolumineszenzvornchtitch by sublimation.
- the compounds according to the invention are also readily soluble in organic solvents, in particular in polar organic solvents. This leads to a simplified purification during the synthesis of the complexes. Furthermore, the complexes according to the invention can thereby be used for the preparation of OLEDs in solution-processed processes, for example printing processes.
- the solvents and reagents used can, for. From Sigma-ALDRICH or ABCR. Ligand Synthesis
- 2-Bromo-N-phenylaniline is prepared by reacting 1-iodo-2-bromo-benzene with aniline using Pd (OAc) 2 (0.005 equivalent), POP (bis [2- (diphenylphosphanyl) phenyl] ether). (0.0075 equivalents) and NaOtBu (1.4 equivalents) in toluene at 130 ° C over 18 hours (according to M. Buden et al., J. Org. Chem. 2009, 74 (12), 4490-4498). b) Synthesis of NHA
- the autoclave is closed and the contents are stirred for 24 h at 100.degree.
- the reaction mixture is taken up in dichloromethane, washed three times with H 2 O, then the aqueous phase is extracted three times with 30 ml of dichloromethane, the organic phase is dried over MgSO 4 and concentrated in vacuo. The residue is separated in a silica gel column.
- the compounds of the invention can be processed from solution.
- the production of such components is based on the production of polymeric light-emitting diodes (PLEDs), which has already been described many times in the literature (eg in WO 2004/037887).
- the structure is composed of substrate / ITO / PEDOT (80 nm) / interlayer (80 nm) / emission layer (60 nm) / ETL (30 nm) / cathode. These are substrates of Company Technoprint (Sodalimeglas) on which the ITO structure (indium tin oxide, a transparent, conductive anode) is applied.
- PEDOT is a polythiophene derivative (Baytron P VAI 4083sp.) From HC Starck, Goslar, which is supplied as aqueous dispersion) is also applied by spin coating in the clean room as buffer layer.
- the required spin rate depends on the degree of dilution and the specific spin coater geometry (typically 80 nm: 4500 rpm).
- the substrates are baked for 10 minutes at 180 ° C on a hotplate.
- the interlayer used is for hole injection.
- the intet layer can also be replaced by one or more layers, which merely have to fulfill the condition that they are not replaced by the downstream processing step of the EML deposition from solution.
- the emitters according to the invention are dissolved together with the matrix materials in toluene.
- the typical solids content of such solutions is between 16 and 25 g / L, if, as here, the typical for a device layer thickness of 60 nm is to be achieved by spin coating.
- the solution-processed devices contain an emission layer of (polystyrene: M1: M2: emitter) (20%: X%: Y%: 10%).
- the emission layer is spin-coated in an inert gas atmosphere, in this case argon, and baked at 130 ° C. for 30 minutes. Then an electron transport layer (ETL) (ETM1: ETM2) (50%: 50%) is evaporated in vacuo. Finally, a cathode of aluminum (100 nm) ( "6 mbar high purity metals from Aldrich, coaters of Lesker oa, typically Aufdampfdruck 5 x 10) by vapor deposition.
- ETL electron transport layer
- FIG. 1 Single-crystal structure of [Cu (NHA) (xantphos)] from Example 3
- FIG. 2 Luminescence properties of [Cu (NHA) (xantphos)] from Example 3: a) Luminescence in the solid: The solid shows red emission with an emission maximum at 609 nm. B) Luminescence in solution in dichloromethane: The solution shows red
- Luminescence in a polystyrene matrix The compound in a polystyrene matrix shows red emission with an emission maximum at 594 nm.
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Abstract
Description
Claims
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DE112016005635.4T DE112016005635A5 (en) | 2015-12-10 | 2016-11-18 | METAL COMPLEX |
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