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Definitions

• the present invention relates to compounds which are suitable for use in electronic devices. Furthermore, the present invention relates to processes for their preparation and electronic devices.
• Organic-based charge transport materials for example triarylamine-based hole transporters
• OLEDs or PLEDs organic or polymeric light-emitting diodes
• O-SC organic solar cells
• O-FET organic field-effect transistors
• O-TFT organic thin-film transistors
• O-IC organic switching elements
• O-lasers organic laser diodes
• charge injection layer for example, to compensate for unevenness of the electrode (“planarization layer”), often of a conductive, doped polymer,
• the above arrangement represents the general structure of an organic electronic device, wherein different layers can be combined, so that in the simplest case an arrangement of two electrodes results, between which an organic layer is located.
• the organic layer in this case fulfills all functions, including the emission of light in the case of OLEDs.
• Such a system is described, for example, in WO 90/13148 A1 on the basis of poly (p-phenylenes).
• the object of the present invention is therefore to provide new compounds which lead to electronic devices with improved properties.
• the object is to provide hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron blocking materials and / or emitter materials which exhibit improved properties in terms of efficiency, operating voltage, lifetime, color coordinates and / or color purity, ie emission band width.
• the compounds should be as easy as possible to process, in particular show a good solubility and film formation. Another task can be seen in electronic
• the electronic devices should be used or adapted for many purposes.
• the performance of the electronic devices should be maintained over a wide temperature range.
• the invention thus relates to a compound comprising at least one structure of the formulas (I) and / or (II)
• X is the same or different CR or N at each occurrence;
• E is a divalent bridge, wherein the group E together with the C atoms connected thereto forms a five- or six-membered ring;
• R 1 is the same or different H, D, F, Cl, Br, I at each occurrence
• R 2 is the same or different at each occurrence, H, D, F or a
• aliphatic, aromatic and / or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, in which also one or more H atoms may be replaced by F;
• substituents R 2 may also form a mono- or polycyclic, aliphatic ring system ..
• adjacent carbon atoms or adjacent "CH 2 groups” means that the carbon atoms are bonded directly to one another.
• 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.
• aryl group or heteroaryl either a simple aromatic cycle, 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 C 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 context of this invention is a system which does not necessarily contain only aryl or heteroaryl groups, but in which also several aryl or heteroaryl groups by a non-aromatic moiety (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.
• systems in which two or more aryl or heteroaryl groups are bonded directly to each other, such as.
• biphenyl or terphenyl also be understood as an aromatic or heteroaromatic ring system.
• a cyclic alkyl, alkoxy or thioalkoxy group is understood as meaning a monocyclic, a bicyclic or a polycyclic group.
• a C 1 - to C 40 -alkyl group in which also individual H atoms or CH 2 groups can be substituted by the abovementioned groups for example the radicals methyl, ethyl, n-propyl, 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-h
• alkenyl group is understood as meaning, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl.
• alkynyl group is meant, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl.
• o-alkoxy group for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy or 2-methylbutoxy understood.
• 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- indenofluorene, cis- or trans-monobenzoindenofluorene, cis-
• Formula (Ib-1) Formula (IIb-1) most preferably, wherein the symbols used have the meanings given above.
• Formula (Ic) is preferred, wherein the symbols used have the meanings mentioned above and E may be the same or different at each occurrence.
• the compounds have at least two bicyclic groups which are formed by a structural element comprising a group Y, where Y can be identical or different in each occurrence and has the abovementioned meaning.
• the compound may preferably have structures of the formula CyE- (CyF) n , where the following applies to the symbols and indices:
• n 2 or 3
• CyE is a structural element selected from the formulas
• CyE-25 (CyE-25) (CyE-26) (CyE-27) and CyF is at least one structural element selected from the formulas
• Invention is U equal to O.
• CyF is at least one structural element selected from the formulas
• the compounds have structures of the formula CyG (CyH) n , where CyG and CyH in each case span a ring and the symbols and indices apply to:
• n 2 or 3
• CyG is a structural element selected from the formulas
• a maximum of three symbols X in CyG and / or CyH stands for N, more preferably at most two symbols X in CyC represent N, very particularly preferably at most one symbol X in CyC stands for N. More preferably, all symbols X stand for CR.
• CyG are the groups of the following formulas (CyG-6) to (CyG-28),
• aromatic ring atoms which may each be substituted by one or more radicals R 1; two adjacent radicals R or R with R 1 can also form a mono- or polycyclic, aliphatic or aromatic ring system with one another.
• these radicals R at each occurrence are identically or differently selected from the group consisting of H, D, F, N (R) 2 , a straight-chain alkyl group having 1 to 6 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, wherein one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which may be substituted by one or more radicals R 1 ; it can have two adjacent Radicals R or R with R 1 also together form a mono- or polycyclic, aliphatic or aromatic ring system.
• the compounds according to the invention comprising structures of the formula (I) and / or (II) may also be chiral, depending on the structure. This is particularly the case when they contain substituents, for example alkyl, alkoxy, dialkylamino or aralkyl groups, which have one or more stereocenters. Since the basic structure of the complex can also be a chiral structure, the formation of diastereomers and several pairs of enantiomers is possible. The compounds according to the invention then comprise both the mixtures of the different diastereomers or the corresponding racemates and also the individual isolated diastereomers or enantiomers.
• the compound may be in the form of an enantiomeric mixture, more preferably a diastereomeric mixture.
• an enantiomeric mixture more preferably a diastereomeric mixture.
• the structures of the formulas (I) and / or (II) preferably have a bromine atom content of at most 18% by weight, more preferably at most 10% by weight and especially preferably at most 5% by weight , According to a preferred aspect of the present invention, the compounds according to the invention preferably have a bromine atom content of at most 18% by weight, more preferably at most 10% by weight and especially preferably at most 5% by weight.
• Particularly preferred compounds include structures according to the following formulas 1 to 59:
• particularly preferred compounds comprise structures according to the following formulas 60 to 67:
• the compounds having at least one structure of the formulas 60, 61, 64 to 67 may preferably be present in the form of a diastereomer mixture and / or used.
• the compounds having at least one structure of the formulas 68 to 77 may preferably be present in the form of a diastereomer mixture and / or used.
• particularly preferred compounds include structures according to the following formulas 78 to 85:
• the compounds according to the invention can in principle be prepared by various methods. However, they have the following
• another object of the present invention is a process for preparing the compounds comprising structures of the formula (I) and / or (II) by reacting at least one aldehyde with at least one aromatic or heteroaromatic amine and at least one bicyclic olefin.
• at least one aldehyde with at least one aromatic or heteroaromatic amine and at least one bicyclic olefin.
• pure substances are reacted to obtain a defined product.
• the compounds of the invention are preferably by
• reaction sequence imine formation and Povarov reaction can be carried out preferably as a one-pot process.
• activated olefins find bi- and tri-cyclic olefins, for example, the bicyclo [2.2.1] - (norbornene) and bicyclo [2.2.2] type (barrels) use.
• Lewis acids are skin group element compounds such as boron, aluminum, gallium and indium halides and their adducts, particularly preferably boron trifluoride, boron trifluoride etherates,
• Transition metal and lanthanoid compounds preferably Zr, Cu, Ag, Au, Zn, Y, La, Yb salts, such as halides, acetates and triflates, are used.
• the dehydrogenation of the substituted tetrahydroisoquinoline can be carried out by literature methods, e.g. by transition metal-catalyzed dehydrogenation or transfer dehydrogenation, or by oxidation with
• Metal oxides e.g., manganese dioxide
• quinones e.g., DDQ
• aldehydes may have one, preferably two or more
• Aldehyde groups can be used, preferably using aromatic or heteroaromatic aldehydes.
• aldehydes are, inter alia, the compounds set forth in the Synthesis Examples.
• preferred monoaldehydes include benzaldehyde (CAS 100-52-7), alkylaldehyde-substituted benzaldehydes, 2-naphthaldehyde (CAS 66-99-9), 6-tert-butyl-3-formylpyridine (CAS 391900- 69-9).
• dialdehydes include 1, 3-phthalaldehyde (CAS 626-19-7), 1, 4-phthalaldehyde (CAS 623-27-8),
• aromatic or heteroaromatic amines having one, preferably two or more amine groups may be used.
• aromatic or heteroaromatic amines include, among others, the compounds set forth in the Synthetic Examples.
• the preferred monoamines include, for example, aniline (CAS 62- 63-3), 4-methylaniline (CAS 106-49-0), 3,5-di-methylaniline, 4-t-butylaniline (CAS 769-92-6), 4-phenylaniline (CAS 92-67-1), 2-tert-butyl-5-aminopyrimidine (CAS 59950-55-9), 2-benzofuranamine (CAS 139266-08-3), 2-aminobenzo [b] thiophene ( CAS 4521-30-6), 1-aminonaphthalene (CAS 134-32-7), 8-aminoquinoline (CAS 578-66-5), 1-anthracenamine (CAS 610- 49-1), 2-anthracenamine (CAS 613 -13-8) and 1-phenazinamine (9CI) (CAS 2876-22-4).
• aniline CAS 62- 63-3
• 4-methylaniline CAS 106-49-0
• 3,5-di-methylaniline 3,5-di-methylaniline
• diamines p-phenylenediamine (CAS 06-50-3), m-phenylenediamine (CAS 108-45-2), o-phenylenediamine (CAS 95-54-5), 1,5-naphthalenediamine (CAS 2243-62-1) and 1,5-naphthyridine-4,8-diamine (CAS 64761-26-8).
• bicyclic olefins may have one, two or more
• olefins are those in the synthesis examples
• bicyclic olefins include, among others
• Norbornene (CAS 498-66-8), norbornadiene (CAS 121-46-0), 7,7-dimethyl norbornene (CAS 6541-60-2), benzonorbornadiene (CAS 4453-90-1), 7-oxanorbomene (CAS 6705-50-6), 7-oxabenzonorbornadiene (CAS 573-57-9), bicyclo (2,2,2) -2-octene (CAS 931-64-6), bicyclo (2,2,2) octa- 2,5-diene (CAS 500-23-2), bicyclo (2,2,2) octa-2,5,7-triene (CAS 500-24-3) and 1,4-dihydro-1, 4- Ethenonaphthalene (CAS 7322-47-6).
• a Lewis acid can be used as a catalyst, with advantage Bortrifluoridetherat (CAS 60-29-7) can be used.
• Oxidizing agents such as manganese dioxide or quinones suitable.
• An intermediate compound obtained after the reaction of at least one aldehyde with at least one aromatic amine and at least one bicyclic olefin can be reacted in a coupling reaction.
• Suitable reactions for forming C-C bonds and / or C-N bonds are known to those skilled in the art and described in the literature. Particularly suitable and preferred coupling reactions which all lead to C-C linkages are those according to BUCHWALD, SUZUKI, YAMAMOTO, SILENCE, HECK, NEGISHI, SONOGASHIRA and HIYAMA. By these methods, optionally followed by purification, such. B. recrystallization or sublimation, the compounds of the invention, comprising structures of formula (I) and / or formula (II) in high purity, preferably more than 99% (determined by 1 H-NMR and / or HPLC).
• the compounds of the invention may also be suitable
• substituents for example by longer alkyl groups (about 4 to 20 carbon atoms), in particular branched alkyl groups, or
• aryl groups for example xylyl, mesityl or branched terphenyl or quaterphenyl groups containing a
• Solubility in common organic solvents cause, such as Toluoi or xylene at room temperature in sufficient
• Concentration soluble to process the complexes from solution are particularly suitable for processing from solution, for example by printing processes.
• the compounds of the invention comprising at least one structure of the formulas (I) and / or (II) already have an increased solubility in these solvents.
• the compounds of the invention may also be mixed with a polymer. It is also possible to incorporate these compounds covalently into a polymer. This is particularly possible with compounds which are substituted with reactive leaving groups, such as bromine, iodine, chlorine, boronic acid or boronic acid esters, or with reactive, polymerizable groups, such as olefins or oxetanes.
• oligomers can be used as monomers for the production of corresponding oligomers, dendrimers or polymers.
• the oligomerization or polymerization is preferably carried out via the halogen functionality or the boronic acid functionality or via the polymerizable group. It is also possible to crosslink the polymers via such groups.
• the compounds of the invention and polymers can be used as a crosslinked or uncrosslinked layer.
• Polymer, oligomer or dendrimer are present. Depending on the linkage of the structures of the formulas (I) and / or (II) or of the compounds, these therefore form a side chain of the oligomer or polymer or are linked in the main chain.
• the polymers, oligomers or dendrimers may be conjugated, partially conjugated or non-conjugated.
• the oligomers or polymers may be linear, branched or dendritic.
• the monomers according to the invention are homopolymerized or copolymerized with further monomers.
• Preferred are copolymers, wherein the units according to
• Suitable and preferred comonomers which form the polymer backbone are selected from fluorenes (for example according to EP 842208 or WO 2000/022026), spirobifluorenes (for example according to EP 707020, EP 894107 or WO 2006/061181), para phenylenes (for example in accordance with WO 92/18552), carbazoles (for example according to WO 2004/070772 or WO 2004/113468), thiophenes (for example according to EP 1028136), dihydrophenanthrenes (eg.
• WO 2005/014689 cis-and trans-indeno-fluorenes (eg according to WO 2004/041901 or WO 2004/113412), ketones (eg according to WO 2005/040302), phenanthrenes (eg . according to
• the polymers, oligomers and dendrimers may also contain other units, for example hole transport units, in particular those based on triarylamines, and / or electron transport units.
• the present compounds can be a relatively low
• Another object of the present invention is accordingly a compound having a molecular weight of W
• - 46 - preferably at most 10,000 g / mol, more preferably at most 5000 g / mol and especially preferably at most 3000 g / mol.
• preferred compounds are characterized in that they are sublimable. These compounds generally have a molecular weight of less than about 200 g / mol.
• the compounds according to the invention may have at least one metal atom selected from iridium, ruthenium, palladium, platinum, osmium or rhenium, preferably iridium or platinum.
• Compounds are particularly suitable as phosphorescent emitters.
• the compounds 1 to 27 set forth above and the compounds A1 to A27 set forth in Examples can be reacted with platinum and / or iridium metal complexes to be emitted.
• M is iridium or platinum
• L is the same or different at each occurrence a ligand
• co-ligand is 2 or 3; m is 0, 1, 2, 3 or 4;
• [IrCl 2 (acac) 2] ' for example Na [IrCl 2 (acac) 2 ]
• Metal complexes with acetylacetonate derivatives as a ligand for example, lr (acac) 3 or tris (2,2,6,6-tetramethylheptane-3,5-dionato) iridium, and IrC xhfeO, where x is usually a number between 2 and 4 ,
• Suitable platinum starting materials are, for example, PtCl 2 , K 2 [PtCl 4 ],
• Heteroleptic complexes can also be used, for example, according to WO
• 2005/042548 be synthesized.
• the synthesis can be activated, for example, thermally, photochemically and / or by microwave radiation.
• the reaction is carried out without the use of an additional solvent in the melt.
• melt means that the ligand is molten and the metal precursor is dissolved or suspended in this melt, and to activate the reaction, it is also possible to add a Lewis acid, for example a silver salt or AlC.
• Yet another object of the present invention is a formulation comprising a compound of the invention or an oligomer according to the invention, polymer or dendrimer 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.
• compositions comprising a compound according to the invention and at least one further organically functional material selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conductor materials, Hole injection materials, electron blocking materials and hole blocking materials.
• the above-described compound comprising structures of the formulas (I) and / or (II) or the above-mentioned preferred embodiments may preferably be used as the active component in an electronic device.
• 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 contains anode, cathode and at least one layer which contains at least one compound comprising structures of the formulas (I) and / or (II).
• 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
• O-LETs organic solar cells
• O-SCs organic optical detectors
• O-FQDs organic field quench devices
• LECs light-emitting electrochemical cells
• O-lasers organic laser diodes
• organic or inorganic materials which are introduced between the anode and cathode, for example charge injection, charge transport or charge blocking materials, but especially emission materials and matrix materials.
• the compounds of the invention show particularly good properties as emission material in
• organic electroluminescent devices A preferred embodiment of the invention are therefore organic electroluminescent devices.
• the compounds according to the invention can be used for the production of singlet oxygen or in photocatalysis.
• the organic electroluminescent device includes cathode, anode and at least one emitting layer. In addition to these layers, 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 M0O 3 or WO 3 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.
• Used compounds that can fluoresce or phosphoresce are particularly preferred.
• the three layers exhibiting blue, green and orange or red emission (for the basic structure see, for example, WO 2005/011013) or systems having 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 contains the compound according to the invention comprising structures of the formula (I) and / or (II) or the abovementioned preferred embodiments as an emitting compound and / or as a matrix material in one or more emitters Layers, preferably in combination with a further matrix material and / or a further emitting compound.
• Structures according to formula (I) and / or (II) are used as the emitting compound in an emitting layer, preferably in combination with a matrix material which comprises compounds having structures according to formula (I) or (II). Furthermore, an inventive
• Metal complex comprising structures of the formula (I) and / or (II) are combined with a matrix material without structures of formula (I) and / or (II). Furthermore, a compound according to the invention comprising structures according to formula (I) and / or (II) can be used as matrix material, which matrix material can be combined with a metal complex without structures of formula (I) and / or (II).
• the compound according to the invention comprising structures according to formula (I) and / or (II) is used as the emitting compound in an emitting layer, it is preferably used in combination with one or more matrix materials.
• the mixture of the compound according to the invention comprising structures of the formula (I) and / or (II) and the matrix material contains between 0.1 and 99% by volume, preferably between 1 and 90% by volume, more preferably between 3 and 40 % By volume, in particular between 5 and 15% by volume, of the compound according to the invention comprising structures of the formula (I) and / or (II) based on the total mixture of emitter and matrix material. Accordingly, the mixture contains between 99.9 and 1% by volume, preferably between 99 and 10% by volume, more preferably between 97 and 60% by volume, in particular between 95 and 85% by volume 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 compounds according to the invention are ketones, phosphine oxides, sulfoxides and sulfones, for. B. according to
• WO 2010/006680 triarylamines, carbazole derivatives, z. B. CBP (N, N-bis-carbazolylbiphenyl), m-CBP or in WO 2005/039246,
• bipolar matrix materials e.g. B. according to
• emmit Schlierenden compounds are used, which comprise at least one structure according to formulas (I) and / or (II), as well as with
• emmit Schlierenden compounds which have no structure according to formulas (I) and / or (II).
• the aforementioned ratios of matrix material to emmit Schlden compounds apply accordingly.
• 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 one 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 comprise
• Structures according to formula (I) and / or (II) are used as a co-matrix for longer-wave emitting triplet emitters, for example for green or red emitting triplet emitters.
• the compounds of the invention can also be used in others
• the complexes according to the invention can be used as matrix material for other phosphorescent metal complexes in an emitting layer.
• an electronic device preferably an organic electroluminescent device, is the subject of the present invention, which comprises one or more compounds according to the invention and / or at least one oligomer, polymer or dendrimer according to the invention in one or more electron-conducting layers
• an electronic device preferably an organic electroluminescent device
• an organic electroluminescent device which comprises one or more compounds according to the invention and / or at least one oligomer, polymer or dendrimer according to the invention in one or more hole-conducting layers, particularly preferably as a hole-conducting compound.
• the cathode 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.).
• alloys of an alkali or alkaline earth metal and silver for example an alloy of magnesium and silver.
• 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. It may also be preferred between a metallic cathode and the
• organic semiconductors to introduce 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, Li 2 O, BaF 2) MgO, NaF, CsF, CS 2 CO 3, etc.).
• organic alkali metal complexes for.
• B. Liq (lithium quinolinate). The layer thickness of this layer is preferably between 0.5 and 5 nm.
• the anode 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, are suitable for this purpose.
• metal / metal oxide electrodes eg Al / Ni / NiO x , Al / PtO x
• at least one of the electrodes must be transparent or partially transparent to allow either the irradiation of the organic material (O-SC) or the outcoupling of light (OLED / PLED, O-LASER).
• Preferred anode materials here are conductive mixed metal oxides.
• ITO indium tin oxide
• IZO indium zinc oxide
• conductive, doped organic materials in particular conductive doped polymers, for. B. PEDOT, PANI or derivatives of these polymers.
• p-doped hole transport material is applied to the anode as a hole injection layer, wherein as p-dopants metal oxides, for example M0O 3 or WO 3 , or (per) fluorinated electron-poor Aromatics are suitable.
• p-dopants are HAT-CN (hexacyano-hexaazatriphenylene) or the compound NPD9 from Novaled. Such a layer simplifies the hole injection in materials with a low HOMO, that is, a HOMO of large magnitude.
• 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 electronic device in particular an organic electroluminescent device, characterized in that one or more layers are coated with a sublimation process.
• the materials in vacuum sublimation are at an initial pressure of usually less than 10 -5 mbar, preferably less than 10 'deposited 6 mbar. It is also possible that the initial pressure is even lower or even higher, for example less than 10 "7 mbar.
• an electronic device in particular an organic electroluminescent device, characterized in that one or more layers with the OVPD (Organic Vapor Phase Deposition) method or with the aid of a carrier gas sublimation
• OVPD Organic Vapor Phase Deposition
• Method is the OVJP (Organic Vapor Jet Printing) method, in which the materials are applied directly through a nozzle and thus structured (for example, M. S. Arnold et al., Appl. Phys. Lett., 2008, 92, 053301).
• OVJP Organic Vapor Jet Printing
• an electronic device in particular an organic electroluminescent device, characterized in that one or more layers of solution, such as. B. by spin coating, or with any printing process, such.
• a printing process such as 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
• soluble compounds are necessary, which are obtained for example by suitable substitution.
• the electronic device in particular the organic electroluminescent device, can also be produced as a hybrid system by applying one or more layers of solution and vapor-depositing one or more other layers.
• an emissive layer comprising a compound according to the invention comprising structures of the formula (I) and / or (II) and a matrix material of solution and then evaporate a hole blocking layer and / or an electron transport layer in vacuo.
• organic electroluminescent devices comprising compounds according to the invention comprising structures of the formula (I) and / or (II) or the preferred embodiments listed above.
• the electronic devices according to the invention are distinguished by one or more of the following surprising advantages over the prior art:
• Electronic devices in particular organic electroluminescent devices containing compounds, oligomers, polymers or dendrimers having structures of the formula (I) and / or (II) as emissive materials, as electron-conducting materials or as hole-conducting materials have a very good lifetime.
• W organic electroluminescent devices containing compounds, oligomers, polymers or dendrimers having structures of the formula (I) and / or (II) as emissive materials, as electron-conducting materials or as hole-conducting materials have a very good lifetime.
• Electronic devices in particular organic electroluminescent devices containing compounds, oligomers, polymers or dendrimers having structures of the formula (I) and / or (II) as emissive materials, as electron-conducting materials or as hole-conducting materials have an outstanding efficiency. In particular, the efficiency is significantly higher than analogous compounds containing no structural unit of formula (I) or formula (II).
• the compounds according to the invention comprising at least one metal atom, preferably selected from Ir or Pt, in some cases have a very narrow emission spectrum, resulting in a high level of emission
• the compounds of the invention, oligomers, polymers or dendrimers having structures of the formula (I) and / or (II) show a very high stability and lead to compounds having a very long lifetime.
• Structures according to formula (I) and / or (II) can be avoided in electronic devices, in particular organic electroluminescent devices, the formation of optical loss channels. As a result, these devices are distinguished by a high PL and thus high EL efficiency of emitters or an excellent energy transfer of the matrices to dopants. 7.
• the use of compounds, oligomers, polymers or dendrimers having structures of the formula (I) and / or (II) in layers of electronic devices, in particular organic electroluminescent devices leads to a high mobility of the electron conductor structures.
• Another object of the present invention is the use of a compound of the invention and / or an oligomer, polymer or dendrimer according to the invention in an electronic device as hole injection material, hole transport material (HTM), hole blocking material (HBM), electron transport material (ETM) electron injection material, electron blocking material and / or emitter material .
• HTM hole transport material
• HBM hole blocking material
• ETM electron transport material
• TTM triplet emitter material
• blue blue
• SEB Singlet emitter
• Manganese dioxide on a Celite layer the manganese dioxide is washed with 1000 ml of ethyl acetate and freed the combined filtrates in vacuo from the solvents. The residue is recrystallized and
• fractional sublimation (p is about 10 "4 - 10 -6 mbar, T 150 - 400 ° C) free of low boilers and non-volatile secondary components compounds having a molecular weight greater than about 1200 g / mol. are preferably freed of solvent residues by annealing in a high vacuum.
• Type A monoaldehyde + monoamine + monoolefin
• Diastereomeric mixture Type F monoaldehyde + monoamine + diolefin
• Type G monoaldehyde + monoamine + triolefin
• the verbs of type A33 ff, B, D, D, E, F and G can be used as e-TMM, HBM, ETM, SMB and SEB.
• Compound A1-A27 may preferably be used as bidentate chelating ligands for transition metals, e.g. Iridium and platinum, and as
• Electron transport material find use.
• the verbs of type A28 ff, B, D, D, E, F and G can be used as electron-conducting triplex matrix material (e-TMM), hole blocking material (HBM), electron transport material (ETM), blue singlet material! (SMB) and blue singlet emitter (SEB) are used
• e-TMM electron-conducting triplex matrix material
• HBM hole blocking material
• ETM electron transport material
• SMB blue singlet material!
• SEB blue singlet emitter
• inventive OLEDs and OLEDs according to the prior art is carried out according to a general method according to WO 2004/058911, based on the circumstances described here
• the following examples introduce the results of different OLEDs.
• Glass slides with structured ITO 50 nm, indium tin oxide
• the OLEDs have the following layer structure: substrate / hole transport port layer 1 (HTL1) consisting of HTM doped with 3% NDP-9
• the cathode is formed by a 100 nm thick aluminum layer.
• the emission layer always consists of at least one matrix material (host material, host material) and an emitting dopant (dopant, emitter) which passes through the matrix material or the matrix materials
• Cover vaporization is mixed in a certain volume fraction.
• the electron transport layer may consist of a mixture of two materials. The exact structure of the OLEDs is shown in Table 1. The materials used to make the OLEDs are shown in Table 4.
• the OLEDs are characterized by default.
• the electroluminescence spectra, the current efficiency (measured in cd / A) and the voltage (measured at 1000 cd / m 2 in V) are determined from current-voltage-brightness characteristics (IUL characteristic curves).
• IUL characteristic curves current-voltage-brightness characteristics
• the service life is determined.
• the lifetime is defined as the time after which the luminance has dropped to a certain level from a certain starting luminance.
• the term LD50 means that the stated lifetime is the time at which the luminance has fallen to 50% of the starting luminance, ie from 1000 cd / m 2 to 500 cd / m 2 .
• LD50 means that the stated lifetime is the time at which the luminance has fallen to 50% of the starting luminance, ie from 1000 cd / m 2 to 500 cd / m 2 .
• different starting brightnesses were chosen.
• the compounds according to the invention can be used inter alia as HTM, TMM, ETM, HBM, SMB and SEB in OLEDs.
• ⁇ fabelte 1 Structure of the OLED
• the iridium complexes according to the invention can also be processed from solution and lead there to process technology significantly simpler OLEDs, in comparison to the vacuum-processed OLEDs, with nevertheless good properties.
• 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 consists of substrate / ITO / PEDOT (80 nm) / interlayer (80 nm) /
• substrates of the company Technoprint Sodalimeglas
• ITO Structure indium tin oxide, a transparent, conductive anode
• the substrates are cleaned in the clean room with DI water and a detergent (Deconex 15 PF) and then activated by a UV / ozone plasma treatment.
• an 80 nm layer of PEDOT PEDOT is a polythiophene derivative (Baytron P VAI 4083sp.) From HC Starck, Goslar, which is supplied as an aqueous dispersion) is also applied in the clean room as a buffer layer by spin-coating.
• 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 hot plate.
• the interlayer used is for hole injection, in this case HIL-012 is used by Merck.
• the interlayer may be replaced by one or more layers, which merely have to fulfill the condition imposed by the downstream one
• the emitters according to the invention are dissolved together with the matrix materials in toluene.
• the typical solids content of such solutions is between 6 and 25 g / L, if, as here, the typical for a device layer thickness of 80 nm is to be achieved by spin coating.
• the solution-processed devices contain an emission layer
• Emission layer is spun in an inert gas atmosphere, in the present case argon, and baked at 130 ° C for 30 min. Finally, a cathode is made of barium (5 nm) and then aluminum (100 nm) (high purity metals from Aldrich, especially barium 99.99% (stock number 474711);

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