Classifications

• • 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
  • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
  • C07F1/08—Copper compounds
• • 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
  • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
  • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
• • 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 Table
  • 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
  • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
  • H10K10/40—Organic transistors
  • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/50—Photovoltaic [PV] devices
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
  • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
• • 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
  • H10K85/361—Polynuclear complexes, i.e. complexes comprising two or more metal centers
• • 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K2101/00—Properties of the organic materials covered by group H10K85/00
  • H10K2101/10—Triplet emission
• • 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
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the invention relates to copper (I) complexes of the general formula A, in particular for use in optoelectronic components.
• Such components consist mainly of organic layers.
• a voltage of z. B. 5 V to 10 V occur from a conductive metal layer, for. B. from an aluminum cathode, electrons in a thin electron conduction layer and migrate toward the anode.
• This consists z. B. from a transparent, but electrically conductive, thin indium tin oxide layer, from the positive charge carriers, so-called. Holes, immigrate into an organic hole conduction layer. These holes move in the opposite direction to the cathode compared to the electrons.
• the emitter layer which also consists of an organic material, are in addition special emitter molecules on which or in the vicinity of the two charge carriers recombine and thereby lead to neutral, but energetically excited states of the emitter molecules.
• the excited states then give off their energy as a bright light emission, e.g. B. in blue, green or red color. Also white-light emission is feasible.
• the emitter layer may also be dispensed with if the emitter molecules are located in the hole or electron conduction layer.
• the present invention was based on the object to provide new compounds that are suitable for optoelectronic devices.
• X * Cl, Br, I, CN, SCN, alkynyl and / or N 3 (ie independently of one another so that the complex can have two identical or two different atoms X *);
• the imine function is part of an N-heteroaromatic ring 5 such as pyrazole, isoxazole, isothiazole, triazole, oxadiazole, thiadiazole, tetrazole, oxatriazole or thiatriazole , is also part of this aromatic group.
• the carbon atom is located both directly adjacent to the imine nitrogen atom and to the E atom.
• ⁇ * ⁇ may optionally be substituted, in particular with at least one group which increases the solubility of the copper (I) complex in the common organic solvents for OLED component production.
• Common organic solvents include, in addition to alcohols, Emern, alkanes and halogenated aliphatic and aromatic hydrocarbons and alkylated aromatic hydrocarbons, especially toluene, chlorobenzene, dichlorobenzene, mesitylene, xylene, tetrahydrofuran, phenetole, propiophenone.
• a copper (I) complex according to the invention consists in a preferred embodiment of three identical ligands ⁇ * ⁇ , which can act directly as a charge transport molecule, whereby different functionalities can be introduced directly via the respective ligands (for example, a hole transport or electron transport unit, hereinafter called hole or electron conductor) and thus an optimal charge carrier transport to and on the copper complex is ensured without these functionalities must be attached via additional units on the periphery of the respective ligands, which reduces the effort of synthesis and thus the cost of production.
• the copper (I) complex according to the invention also preferably has identical atoms X *.
• the great advantage of using copper as a central metal is its low price, especially when compared to the metals commonly used in OLED emitters such as Re, Os, Ir and Pt.
• the low toxicity of copper also supports its use.
• the copper (I) complexes according to the invention are distinguished by a wide range of achievable emission colors.
• the emission quantum yield is high, in particular greater than 50%.
• the emission decay times are surprisingly short.
• inventive copper (I) complexes can be used in relatively high emitter concentrations without significant quenching effects. This means emitter concentrations of 5% to 100% can be used in the emitter layer.
• the ligands ⁇ * ⁇ are preferably pyrazoles, isoxazoles, isothiazoles, 1,2,4-triazoles, 1,2,4-oxadiazoles, 1,2,4-thiadiazoles, tetrazoles, 1,2,3,4 Oxatriazoles and / or 1,2,3,4-thiatriazoles, each of which may be substituted as described herein.
• These ligands can act directly as charge transport molecules, whereby different functionalities can be introduced directly via the respective ligands (for example, a hole transport or electron transport unit, hereinafter referred to as hole transport). or electron conductor) and thus optimal charge carrier transport to and on the copper complex is ensured without these functionalities having to be attached via additional units at the periphery of the respective ligands,
• the ligand is particularly preferably around the following ligands:
• X 0, S or NR 2 ;
• R1-R3 may each independently represent hydrogen, halogen or be substituents on oxygen (-OR), nitrogen (-NR 2) or silicon atoms (-S1R3) are attached, and alkyl (branched or cyclic), aryl , Heteroaryl, alkenyl, alkynyl groups or substituted alkyl (also branched or cyclic), aryl, heteroaryl and alkenyl groups having substituents such as halogens or deuterium, alkyl groups (also branched or cyclic), and others generally known Donor and acceptor groups such as amines, carboxylates and their esters, and CF 3 groups.
• R2-R3 can optionally also lead to fused ring systems.
• the invention also relates to a process for the preparation of a copper (I) complex according to the invention.
• This process according to the invention comprises the step of carrying out a reaction of ⁇ * ⁇ with Cu (I) X *,
• X * Cl, Br, I, CN, SCN, alkynyl and / or N3 (independently of one another);
• N * imine function, which is part of an N-heteroaromatic 5-ring, such as pyrazoles, isoxazoles, isothiazoles, triazole, oxadiazole, thiadiazole, tetrazole, oxatriazole or thiatriazole,
• ⁇ at least one carbon atom, which is also part of the aromatic group, wherein the carbon atom is both directly adjacent to the imine nitrogen atom and to the phosphorus or arsenic atom.
• the optionally present at the ligand ⁇ * ⁇ at least one substituent for increasing the solubility of the complex in organic solvents is described below.
• the reaction is preferably carried out in dichloromethane (DCM), although other organic solvents such as acetonitrile or tetrahydrofuran or dimethyl sulfoxide or ethanol may be used.
• DCM dichloromethane
• organic solvents such as acetonitrile or tetrahydrofuran or dimethyl sulfoxide or ethanol may be used.
• diethyl ether or hexane or methyl tert-butyl ether or pentane or methanol or ethanol or water to the dissolved product, a solid can be recovered. The latter can be carried out by precipitation or indiffusion or in an ultrasonic bath.
• the structure of the formula A is related to known complexes of the form Cu 2 X * 2L 2 L 'or Cu 2 X * 2 L4. Unlike Cu 2 X * 2L 2 L ', however, the complex is accessible in one step by the reaction of Cu (I) X * with the bidentate ⁇ * ligand.
• the complex can be isolated by precipitating with Et 2 O as a yellow or red microcrystalline powder. Single crystals can be obtained by slowly diffusing Et 2 O into the reaction solution. The identities of the complexes were clearly evidenced by elemental and X-ray structural analyzes.
• the bidentate ⁇ * ligands can independently of one another comprise at least one substituent:
• the substituents can each independently be hydrogen, halogen or substituents which are bonded via oxygen (-OR), nitrogen (-NR 2 ) or silicon atoms (-SiR 3 ) and alkyl (also branched or cyclic), aryl, heteroaryl, alkenyl, alkynyl or substituted alkyl (also branched or cyclic), aryl, heteroaryl and alkenyl groups having substituents such as halogens or Deuterium, alkyl groups (also branched or cyclic), and other well-known donor and acceptor groups such as amines, carboxylates and their esters, and CF 3 groups.
• the substituents can optionally also lead to fused ring systems.
• Nonpolar substituents R2-R3 increase the solubility in non-polar solvents and lower the solubility in polar solvents.
• Nonpolar groups are z.
• B. alkyl groups [CH 3 - (CH 2 ) n -] (n 1 - 30), also branched or cyclic, substituted alkyl groups, eg. B. with halogens.
• partially or perfluorinated alkyl groups and perfluorinated oligo- and polyether, z. For example, [- (CF 2 ) 2 -O] n - and (-CF 2 -O) n - (n 2 - 500).
• Polar substituents R2-R3 increase the solubility in polar solvents. These can be:
• Amines -NH 2 , -NR * 2 , -N (CH 2 CH 2 OH) 2 ,
• Negatively charged substituents eg. Borates - (BR * 3 ) - , aluminates - (A1R * 3 ) - (anion may be an alkali metal or ammonium ion).
• At least one of the structures ⁇ * ⁇ is preferably substituted by at least one substituent.
• the substituent may be selected from the group consisting of:
• long-chain, branched or unbranched or cyclic alkyl chains having a length of from Cl to C30, preferably having a length of C3 to C20, particularly preferably having a length of C5 to C15,
• long-chain, branched or unbranched or cyclic, alkoxy chains having a length of Cl to C30, preferably having a length of C3 to C20, particularly preferably having a length of C5 to C15,
• Short-chain polyethers such as. B. polymers of the form (-OCH 2 CH 2 0-) n, where n ⁇ 500. Examples include polyethylene glycols (PEG), which are used as chemically inert, water-soluble and non-toxic polymers with a chain length of 3-50 repeat units can.
• PEG polyethylene glycols
• the alkyl chains or alkoxyl chains or perfluoroalkyl chains are modified in a preferred embodiment of the invention with polar groups, for. B.
• Thiosulfonic acid esters sulfonamides, thiosulfonamides, sulfamides, sulfenamides, sulfates, thiosulfates, sultones, sultams, trialkylsilyl and triarylsilyl groups as well as trialkoxysilyl groups which result in a further increase in solubility.
• the method of presentation may comprise the step of substituting at least one ligand ⁇ * ⁇ with at least one substituent to increase solubility in the desired organic solvent, which substituent in one embodiment of the invention may be selected from o. Groups.
• copper (I) are also complex, which can be prepared by such a synthesis process.
• the copper (I) complexes of the formula A can be used according to the invention as an emitter in an emitter layer of a light-emitting optoelectronic component.
• the optoelectronic components are preferably the following: organic light-emitting components (OLEDs), light-emitting electrochemical cells, OLED sensors (in particular in non-hermetically shielded gas and vapor sensors), organic solar cells, organic field effect transistors, organic lasers and down -Konversions elements.
• OLEDs organic light-emitting components
• OLED sensors in particular in non-hermetically shielded gas and vapor sensors
• organic solar cells organic field effect transistors
• organic lasers organic lasers and down -Konversions elements.
• the copper (I) complexes of the formula A can also be used according to the invention as absorber materials in an absorber layer of an optoelectronic component.
• optical components are understood in particular as:
• OLEDs organic light emitting diodes
• OSCs organic photovoltaics
• OPVs organic photovoltaics
• the proportion of the copper (I) complex in the emitter or absorber layer in such an optoelectronic component is 100% in one embodiment of the invention. In an alternative embodiment, the proportion of copper (I) complex in the emitter or absorber layer is 1% to 99%.
• the concentration of the copper (I) complex as emitter in optical light-emitting components, in particular in OLEDs, is between 1% and 99%, preferably between 1% and 80%.
• the present invention also relates to optoelectronic components which have a copper (I) complex described here.
• the optoelectronic component may be formed as an organic light emitting device, an organic diode, an organic solar cell, an organic transistor, as an organic light emitting diode, a light emitting electrochemical cell, an organic field effect transistor and as an organic laser.
• a method for producing an optoelectronic component in which a copper (I) according to the invention is used in a complex manner the application of such a Copper (I) complex carried on a support material.
• This application can be carried out wet-chemically, by means of colloidal suspension or by sublimation, in particular wet-chemical.
• the method may include the following steps:
• the method may further comprise the step of: applying a third emitter complex dissolved in the first solvent or in a third solvent to the support, wherein the third copper (I) complex is a copper (I) according to the invention complex.
• First and second solvents are not identical.
• a further aspect of the invention relates to a method for changing the emission and / or absorption properties of an electronic component.
• an inventive copper (I) complex is introduced into a matrix material for conducting electrons or holes in an optoelectronic device.
• a further aspect of the invention relates to a use of a copper (I) complex according to the invention, in particular in an optoelectronic component, for converting UV radiation or blue light into visible light, in particular into green, yellow or red light (down conversion).
• a copper (I) complex according to the invention in particular in an optoelectronic component, for converting UV radiation or blue light into visible light, in particular into green, yellow or red light (down conversion).
• the invention relates to a bidentate ligand of the formula B, in particular for the preparation of a copper complex of the formula A, and to the process for preparing such a ligand.
• the bidentate phosphine ligands pyrazole, isoxazole, isothiazole, triazole, oxadiazole, thiadiazole, tetrazole, oxatriazole, thiatriazole were used as described above:
• the ligands were in the case of the pyrazoles, triazoles, oxadiazoles, thiadiazoles, tetrazoles partially prepared according to literature specifications, while the isoxazoles, isothiazoles, oxatriazoles and thiatriazoles are not yet known from the literature and have thus been prepared according to a new synthesis, which is shown below:
• the compounds 2a-j are white, fine-crystalline solids, compound 2k is an orange solid.
• FIG. 2a The crystal structure of FIG. 2a is shown in FIG.
• the photoluminescence (PL) quantum yield of 2a is 80% (measured with Hamamatsu C9920-02G).
• FIGS. 4a and 4b The emission spectra of FIGS. 4a and 4b are shown in FIGS. 8 and 9.
• the PL quantum yield of 4a is 63%, of 4b it is 65%> (measured with Hamamatsu C9920-02G).
• Compound 6a is a yellow, finely crystalline solid.
• the emission spectrum of 6a is shown in FIG.
• Compound 8a is a white, fine crystalline solid.
• the emission spectrum of 8a is shown in FIG.
• the copper (I) complexes according to the invention are distinguished, in particular, by emission toward the blue or into the blue emission region.

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• 2011
  • 2011-08-26 EP EP11179099A patent/EP2540730A1/de not_active Withdrawn
• 2012
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