DE102013008189A1 - metal complexes - Google Patents

Abstract

The present invention relates to metal complexes according to formula (1), their use in electronic devices and electronic devices, in particular organic electroluminescent devices containing these metal complexes.

Description

The present application relates to metal complexes, the use of these metal complexes in electronic devices and electronic devices, in particular organic electroluminescent devices containing these metal complexes.

The construction of organic electroluminescent devices (OLEDs) in which organic semiconductors are used as functional materials is described, for example, in US Pat US 4539507 . US 5151629 . EP 0676461 and WO 98/27136 described. In this case, increasingly used as the emitting materials organometallic complexes that show phosphorescence instead of fluorescence ( MA Baldo et al., Appl. Phys. Lett. 1999, 75, 4-6 ). For quantum mechanical reasons, up to four times energy and power efficiency is possible using organometallic compounds as phosphorescence emitters. In general, there is still room for improvement in OLEDs that show triplet emission. Thus, the physical properties of phosphorescent OLEDs in terms of efficiency, operating voltage and lifetime are still not sufficient for the use of triplet emitters in high-quality and durable electroluminescent devices. This applies in particular to OLEDs which emit in the shorter-wave range, that is to say green and in particular blue. So far, no blue emitting triplet emitter are known, which meet the technical requirements for industrial application.

According to the state of the art, iridium and platinum complexes are mostly used in phosphorescent OLEDs as triplet emitters. However, these have the disadvantage that these are metals with a very low frequency and therefore also corresponding to expensive metals. To protect the natural resources of these metals, it would therefore be desirable to have emitters based on other metals available. Another disadvantage of the commonly used iridium and platinum complexes is that they are mostly organometallic complexes with metal-carbon bonds. Such metal-carbon bonds are sometimes difficult to access synthetically.

Furthermore, these complexes sometimes have only a low thermal stability.

Even with matrix materials, for example materials based on zinc complexes, or electron conductors, for example based on aluminum complexes, further improvements are desirable.

The object of the present invention is therefore to provide metal complexes which are suitable as emitters, as matrix materials, as electron conductors or in other functions for use in OLEDs which have a high thermal stability which, when used in OLEDs, leads to high efficiencies and long lifetimes lead and which are synthetically easily accessible.

Surprisingly, it has been found that certain metal chelate complexes described in more detail below achieve this object and are very suitable for use in organic electroluminescent devices, in particular when used as an emitting material. They show a long service life, high efficiency and good stability against thermal stress. Furthermore, the central atom of these complexes is not iridium or platinum as rare metals. Another advantage of these complexes is that they are synthetically easily accessible. These complexes as well as electronic devices, in particular organic electroluminescent devices containing these complexes are therefore the subject of the present invention.

wobei für die verwendeten Symbole und Indizes gilt:
M ist ausgewählt aus Cu, Ag, Au, Zn oder Al;
A ist ausgewählt aus N oder P;
Y ist bei jedem Auftreten gleich oder verschieden eine bivalente Gruppe, ausgewählt aus CR₂, O, S, 1,2-Vinylen, 1,2- oder 1,3-Phenylen oder eine ortho-verknüpfte Heteroarylengruppe mit 5 oder 6 aromatischen Ringatomen, wobei diese Gruppen jeweils mit einem oder mehreren Resten R substituiert sein kann;
L¹, L², L³ ist gleich oder verschieden bei jedem Auftreten eine Heteroarylgruppe mit 5 bis 25 aromatischen Ringatomen, die mit einem oder mehreren Resten R substituiert sein kann und die ein Stickstoff-, Schwefel- oder Sauerstoffatom enthält, welches an M koordinieren kann, oder eine Aryl- oder Heteroarylgruppe mit 5 bis 18 aromatischen Ringsatomen, die mit einem oder mehreren Resten R substituiert sein kann und die ein exocyclisches Donoratom, ausgewählt aus N, O, S oder P, aufweist, welches an M koordiniert und welches durch einen oder mehrere Reste R substituiert sein kann;
n ist bei jedem Auftreten gleich oder verschieden 0, 1, 2, 3, 4 oder 5;
R ist bei jedem Auftreten gleich oder verschieden H, D, F, Cl, Br, I, N(R¹)₂, CN, NO₂, OR¹, Si(R¹)₃, B(OR¹)₂, C(=O)R¹, P(=O)(R¹)₂, S(=O)R¹, S(=O)₂R¹, OSO₂R¹, eine geradkettige Alkyl-, Alkoxy- oder Thioalkoxygruppe mit 1 bis 40 C-Atomen oder eine verzweigte oder cyclische Alkyl-, Alkoxy- oder Thioalkoxygruppe mit 3 bis 40 C-Atomen oder eine Alkenyl- oder Alkinylgruppe mit 2 bis 40 C-Atomen, die jeweils mit einem oder mehreren Resten R¹ substituiert sein kann, wobei eine oder mehrere nicht benachbarte CH₂-Gruppen durch R¹C=CR¹, C≡C, Si(R¹)₂, C=O, C=S, C=NR¹, P(=O)(R¹), SO, SO₂, NR¹, O, S oder CONR¹ ersetzt sein können und wobei ein oder mehrere H-Atome durch F, Cl, Br, I, CN oder NO₂ ersetzt sein können, oder ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 60 aromatischen Ringatomen, das jeweils durch einen oder mehrere Reste R¹ substituiert sein kann, oder eine Aryloxy-, Heteroaryloxy-, Aralkyl- oder Heteroaralkylgruppe mit 5 bis 60 aromatischen Ringatomen, die durch einen oder mehrere Reste R¹ substituiert sein kann, oder eine Diarylaminogruppe, Diheteroarylaminogruppe oder Arylheteroarylaminogruppe mit 10 bis 40 aromatischen Ringatomen, welche durch einen oder mehrere Reste R¹ substituiert sein kann; dabei können zwei oder mehrere Substituenten R auch miteinander ein mono- oder polycyclisches, aliphatisches, aromatisches, heteroaromatisches und/oder benzoannelliertes Ringsystem bilden;
R¹ ist bei jedem Auftreten gleich oder verschieden H, D, F, Cl, Br, I, N(R²)₂, CN, NO₂, OH, Si(R²)₃, B(OR²)₂, C(=O)R², P(=O)(R²)₂, S(=O)R², S(=O)₂R², OSO₂R², eine geradkettige Alkyl-, Alkoxy- oder Thioalkoxygruppe mit 1 bis 40 C-Atomen oder eine verzweigte oder cyclische Alkyl-, Alkoxy- oder Thioalkoxygruppe mit 3 bis 40 C-Atomen oder eine Alkenyl- oder Alkinylgruppe mit 2 bis 40 C-Atomen, die jeweils mit einem oder mehreren Resten R² substituiert sein kann, wobei eine oder mehrere nicht benachbarte CH₂-Gruppen durch R²C=CR², C≡C, Si(R²)₂, C=O, C=S, C=NR², P(=O)(R²), SO, SO₂, NR², O, S oder CONR² ersetzt sein können und wobei ein oder mehrere H-Atome durch F, Cl, Br, I, CN oder NO₂ ersetzt sein können, oder ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 60 aromatischen Ringatomen, das jeweils durch einen oder mehrere Reste R² substituiert sein kann, oder eine Aryloxy-, Heteroaryloxy-, Aralkyl- oder Heteroaralkylgruppe mit 5 bis 60 aromatischen Ringatomen, die durch einen oder mehrere Reste R² substituiert sein kann, oder eine Diarylaminogruppe, Diheteroarylaminogruppe oder Arylheteroarylaminogruppe mit 10 bis 40 aromatischen Ringatomen, welche durch einen oder mehrere Reste R² substituiert sein kann; dabei können zwei oder mehrere Substituenten R¹ auch miteinander ein mono- oder polycyclisches, aliphatisches, aromatisches, heteroaromatisches und/oder benzoannelliertes Ringsystem bilden;
R² ist bei jedem Auftreten gleich oder verschieden H, D, F oder ein aliphatischer, aromatischer und/oder heteroaromatischer Kohlenwasserstoffrest mit 1 bis 20 C-Atomen, in dem auch ein oder mehrere H-Atome durch F ersetzt sein können; dabei können zwei oder mehrere Substituenten R² auch miteinander ein mono- oder polycyclisches aliphatisches, aromatisches, heteroaromatisches und/oder benzoannelliertes Ringsystem bilden.The present invention thus provides a compound according to the following formula (1)

where the symbols and indices used are:
M is selected from Cu, Ag, Au, Zn or Al;
A is selected from N or P;
Y is the same or different on each occurrence and is a divalent radical selected from CR ₂ , O, S, 1,2-vinylene, 1,2- or 1,3-phenylene or an ortho-linked heteroarylene group having 5 or 6 aromatic ring atoms, these groups may each be substituted by one or more radicals R;
L ¹ , L ² , L ³ is the same or different each occurrence of a heteroaryl group having 5 to 25 aromatic ring atoms, which may be substituted by one or more radicals R and which contains a nitrogen, sulfur or oxygen atom, which coordinate to M may, or an aryl or heteroaryl group having 5 to 18 aromatic ring atoms, which may be substituted by one or more radicals R and which has an exocyclic donor atom selected from N, O, S or P, which coordinates to M and which by one or more radicals R may be substituted;
n is identical or different 0, 1, 2, 3, 4 or 5 at each occurrence;
R is the same or different H, D, F, Cl, Br, I, N (R ¹ ) ₂ , CN, NO ₂ , OR ¹ , Si (R ¹ ) ₃ , B (OR ¹ ) ₂ , C at each occurrence (= O) R ¹ , P (= O) (R ¹ ) ₂ , S (= O) R ¹ , S (= O) ₂ R ¹ , OSO ₂ R ¹ , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which is substituted by one or more radicals R ¹ wherein one or more non-adjacent CH ₂ groups can be represented by R ¹ C =CR ¹ , C≡C, Si (R ¹ ) ₂ , C =O, C =S, C =NR ¹ , P (= O) ( R ¹ ), SO, SO ₂ , NR ¹ , O, S or CONR ¹ may be replaced and wherein one or more H atoms may be replaced by F, Cl, Br, I, CN or NO ₂ , or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ , or an aryloxy, heteroaryloxy, aralkyl or Heteroaralkylgr uppe with 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ¹ , or a Diarylaminogruppe, Diheteroarylaminogruppe or Arylheteroarylaminogruppe having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R ¹ ; two or more substituents R may also together form a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and / or benzoannellated ring system;
R ¹ is the same or different at each occurrence as H, D, F, Cl, Br, I, N (R ² ) ₂ , CN, NO ₂ , OH, Si (R ² ) ₃ , B (OR ² ) ₂ , C (= O) R ² , P (= O) (R ² ) ₂ , S (= O) R ² , S (= O) ₂ R ² , OSO ₂ R ² , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more radicals R ² where one or more non-adjacent CH ₂ groups can be replaced by R ² C =CR ² , C≡C, Si (R ² ) ₂ , C =O, C =S, C =NR ² , P (OO) ( R ² ), SO, SO ₂ , NR ² , O, S or CONR ² may be replaced and wherein one or more H atoms may be replaced by F, Cl, Br, I, CN or NO ₂ , or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R ² , or an aryloxy, heteroaryloxy, aralkyl or Heteroaralkylgru ppe having from 5 to 60 aromatic ring atoms which may be substituted by one or more radicals R ² , or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having from 10 to 40 aromatic ring atoms which may be substituted by one or more radicals R ² ; two or more substituents R ^{1 may} also together form a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and / or benzoannellated ring system;
R ² is the same or different at each occurrence, H, D, F or an aliphatic, aromatic and / or heteroaromatic hydrocarbon 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 ^{2 may} also together form a mono- or polycyclic aliphatic, aromatic, heteroaromatic and / or benzoannellated ring system.

In this case, the compound of formula (1), if it is a charged compound, nor one or more counterions, which may be the same or different.

The ligand L coordinates via the lone electron pair of the bridgehead A as well as via the partial ligands L ¹ , L ² and L ³ to the metal M. In the context of a partial ligand in the context of the present invention, in the ligand of the formula (2) the groups L ¹ , L ² and L ³ understood, which in each case coordinate to the metal M and are linked to each other via A and optionally via Y. In this case, the partial ligands L ¹ , L ² or L ^{3 can} coordinate to M via a neutral or a negatively charged donor atom, it being possible for this donor atom to be either part of the heteroaryl group or to be bonded exocyclically to an aryl or heteroaryl group.

For the purposes of the present invention, a donor atom is understood to mean an atom which has at least one free electron pair and is therefore capable of binding to a metal ion. In this case, the donor atom can be neutral or negatively charged. Examples of donor atoms that are part of a heteroaryl group are nitrogen, pyrrole, indole or pyridine, oxygen in furan or benzofuran and sulfur in thiophene or benzothiophene.

For the purposes of this invention, an exocyclic donor atom is understood to mean a donor atom which is not part of an aryl or heteroaryl group but which is bonded as a substituent to an aryl or heteroaryl group and which has at least one free electron pair and is therefore capable of to bind a metal ion. In this case, the donor atom can be neutral or negatively charged. Examples of exocyclic donor atoms are oxygen in the form of a phenol or phenolate, sulfur in the form of a thiol or thiolate, nitrogen in the form of an amine, imine, amide or imide and phosphorus in the form of a phosphine.

An aryl group in the sense of this invention contains 6 to 60 C atoms; For the purposes of this invention, a heteroaryl group contains 2 to 60 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. Here, under an 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. A cyclic carbene in the sense of this invention is a cyclic group which binds to the metal via a neutral carbon atom. The cyclic group may be saturated or unsaturated. Arduengo carbenes, ie those carbenes, in which two nitrogen atoms are bonded to the carbene C atom, are preferred here.

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 2 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 also several aryl or heteroaryl groups a non-aromatic moiety (preferably less than 10% of the atoms other than H), such as e.g. As an sp ³ -hybridized C, N or O atom, may be interrupted. For example, 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.

In the context of the present invention, preference is given to taking a C ₁ -C ₄₀ -alkyl group in which individual H atoms or CH ₂ groups may also be substituted by the abovementioned groups, preferably the radicals methyl, ethyl, n-propyl, i Propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, neo-pentyl, cyclopentyl, n -hexyl, neo-hexyl, cyclohexyl, n-heptyl , Cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl and 2,2,2-trifluoroethyl. An alkenyl group is preferably understood as meaning ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl and cyclooctenyl. An alkynyl group is preferably understood to mean ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl and octynyl. A C ₁ - to C ₄₀ -alkoxy group is preferably understood to mean methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy or 2-methylbutoxy. By an aromatic or heteroaromatic ring system having 5-60 aromatic ring atoms, which may be substituted in each case with the abovementioned radicals R and which may be linked via any position on the aromatic or heteroaromatic, are understood in particular groups which are derived from benzene, Naphthalene, anthracene, phenanthrene, benzanthracene, benzphenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, Truxen , Isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6 quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole l, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazine imidazole, quinoxaline imidazole, oxazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, Benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, Pyrazine, phenazine, phenoxazine, phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4- Oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3- Thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, Tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine and benzothiadiazole.

wobei R in dieser Struktur die Ringbildung von Resten R an den Teilliganden L¹, L² und L³ darstellt und die weiteren verwendeten Symbole und Indizes die oben genannten Bedeutungen aufweisen. Dabei weist R die oben genannten Bedeutungen auf, wobei es sich um eine bivalente bzw. trivalente Gruppe handelt, so dass die entsprechenden monovalenten Gruppen wie Halogene nicht in Frage kommen.The partial ligands L ¹ , L ² and L ³ can also be connected to one another via radicals R which are bridged with one another. This results in the complex of formula (1) having a polypodal ligand, cryptates. In the context of this invention, a polypodal ligand is understood as meaning a ligand in which three coordinating partial ligands L ¹ , L ² and L ³ are bound to one another by a group A. The ligand of the compound of formula (1) is therefore a polypodal ligand. For the purposes of this invention, a cryptate is understood as meaning a connection between a cryptand and a metal ion, in which the metal ion is surrounded three-dimensionally by the bridges of the complex-forming cryptand. A cryptand in the context of this invention is understood to mean a macrocyclic tripodal ligand. In this case, a cryptand can arise if all three of the part-ligands L ¹ , L ² and L ³ or if two of the three part-ligands are linked to one another via radicals R. This is shown schematically below:

where R in this structure represents the ring formation of residues R on the partial ligands L ¹ , L ² and L ³ and the other symbols and indices used have the abovementioned meanings. Here, R has the abovementioned meanings, wherein it is a divalent or trivalent group, so that the corresponding monovalent groups such as halogens are not suitable.

In a preferred embodiment of the invention, M is selected from the group consisting of Cu (I), Ag (I), Au (I), Zn (II) and Al (III). Particularly preferred is Cu (I). The value in brackets behind the metal indicates the oxidation state of the metal. These metals are tetrahedral or at least approximately tetrahedral or distorted tetrahedrally coordinated.

When the compound of formula (1) is electrically charged, it still contains one or more counterions, which may be the same or different. When the compound of formula is positively charged (1), the counterion is preferably selected from the group consisting of BF ₄ ^-, PF ₆ ^-, F ^-, Cl ^-, Br ^-, I ^-, NO ₃ ^-, CuCl ₂ ^-, CuBr ₂ ^- , CuI ₂ ^- , B (aryl) ₄ ^- , B (alkyl) ₄ ^- , HSO ₄ ^- , SO ₄ ^2- , PO ₄ ^3- , HCO ₃ ^- , CO ₃ ^2- , BO ₃ ^3- , OCN ^- , SCN ^- , CN ^- , CF ₃ SO ₃ ^- and SbF ₆ ^- . When the compound of the formula (1) is negatively charged, the counter ion is preferably selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , NH ₄ ⁺ , N (aryl ) ₄ ⁺ , N (alkyl) ₄ ⁺ , P (aryl) ₄ ⁺ , P (alkyl) ₄ ⁺ , P [N (CH ₃ ) ₂ ] ₄ ⁺ , S [N (CH ₃ ) ₂ ] ₃ ⁺ and [ C ₁₁ H ₂₄ N] ⁺ (hexamethylpiperidinium), where the alkyl group in each case identically or differently on each occurrence preferably has 1 to 10 C atoms and aryl in each case identical or different at each occurrence for an aryl or heteroaryl group having 5 to 10 aromatic ring atoms stands.

In a preferred embodiment of the invention, the compound of formula (1) is electrically neutral. This is achieved by selecting the charges of the partial ligands L ¹ , L ² and L ³ to compensate for the charge of M. Thus, when M is Cu (I), Ag (I) or Au (I), preferably one of the partial ligands L ¹ , L ² or L ³ coordinates via a negatively charged donor atom and the other partial ligands coordinate via neutral donor atoms. When M is Zn (II), preferably two of the partial ligands L ¹ , L ² or L ³ coordinate via negatively charged donor atoms and the third partial ligand coordinates via a neutral donor atom. When M is Al (III), preferably all three partial ligands L ¹ , L ² and L ³ coordinate via negatively charged donor atoms.

In a preferred embodiment of the invention, the cycle which is formed from A, Y, M and L ¹ or L ² or L ³ , preferably contains 5, 6, 7, 8 or 9 ring atoms. Depending on the exact structure of the partial ligands L ¹ , L ² or L ³ , the index n is correspondingly chosen such that the coordination of M results in a 5-, 6-, 7-, 8- or 9-membered ring. What is meant by the formation of a 5-, 6-, 7-, 8- or 9-membered ring is shown schematically below in some substructures:

In each case, the structure containing one arm of the polypodal ligand and a partial ligand is shown. In all structures depicted, the partial ligand is pyridine and Y is CH ₂ . For the 5-membered ring n = 1, for the 6-membered ring n = 2, etc .. It can be at a different choice of the partial ligands, for example, with n = 0, a 5-membered ring or n = 0 or 1 form a six-membered ring, as shown schematically below:

In the first structure, the part-ligand quinoline and n = 0, in the second structure the part-ligand quinoline, n = 1 and Y = CH ₂ and in the third structure the part-ligand phenanthridine and n = 0.

Particularly preferably, the cycle, which is formed from A, Y, M and L ¹ or L ² or L ³ , contains 6, 7, 8 or 9 ring atoms, more preferably 6, 7 or 8 ring atoms. Which combinations of ring sizes are preferred for the individual part ligands L ¹ or L ² or L ³ depends on the nature of Y. When Y is an aromatic group or when n = 0 and the partial ligand L ¹ or L ² or L ³ binds directly to A, preferred ring sizes are (6-6-6), (5-6-7), ( 6-6-7), (6-7-7) and (7-7-7). Each of these three numbers indicates the ring size that forms the corresponding "arm" of the polypodal ligand with the metal atom. Thus, for example, (5-6-7) means that the cycle formed from A, Y, M and L ¹ , 5 ring atoms and the cycle formed from A, Y, M and L ² , 6 ring atoms and the cycle formed of A, Y, M and L ³ has 7 ring atoms. When Y is aliphatic, the individual arms of the polypodal ligand are not planar and thus somewhat shortened compared to purely aromatic arms, so that the ring sizes (6-6-6) lead here only to a distorted tetrahedron and larger rings are advantageous, in particular the combination of 6-membered with 7- and / or 8-membered rings or combinations of 7- and / or 8-membered rings.

In a preferred embodiment of the invention, L ¹ or L ² or L ^{3 has} 5 to 14 aromatic ring atoms, particularly preferably 5 to 13 aromatic ring atoms, very particularly preferably 5 to 10 aromatic ring atoms. The aryl or heteroaryl groups may be substituted by one or more radicals R, as described above.

wobei R dieselbe Bedeutung hat, wie oben beschrieben, und weiterhin gilt:
X steht bei jedem Auftreten gleich oder verschieden für CR oder N;
D steht bei jedem Auftreten gleich oder verschieden für OH, O^–, SH, S^–, NR₂, NR^–, PR^–, PR₂, OR, SR, COO^–, -C(=O)R, -CR(=NR) oder -N(=CR₂).In a preferred embodiment of the invention, L ¹ , L ² and L ^{3 are the} same or different at each occurrence selected from the groups of the formulas (2) to (41):

where R has the same meaning as described above, and furthermore:
X is the same or different CR or N at each occurrence;
D is the same or different at each occurrence and represents OH, O ^- , SH, S ^- , NR ₂ , NR ^- , PR ^- , PR ₂ , OR, SR, COO ^- , --C (= O) R, --CR (= NR) or -N (= CR ₂ ).

Among these structures, the groups of the formulas (2), (7), (9), (10), (12), (13), (15), (33), (34), (37), ( 39), (40) and (41), and particularly preferred are the groups of the formulas (9), (12), (33), (34), (39), (40) and (41).

The groups of formulas (2) to (41) coordinate to the metal M via the position marked by *. The position indicated by # indicates the position at which the part ligand L ¹ or L ² or L ³ is bound to Y or A, respectively.

Preferably, a maximum of three symbols X in each group represent N, more preferably, at most two symbols X in each group represent N, most preferably, at most one symbol X in each group represents N. More preferably, all symbols X stand for CR.

In a further preferred embodiment of the invention, Y, identical or different at each occurrence, is a divalent group selected from CR ₂ or O, more preferably CR ₂ . When A = N, Y is preferably not O.

In a further preferred embodiment of the invention, the index n is identical or different at each occurrence 0, 1 or 2.

Preferred structures according to formula (1) are structures in which the abovementioned preferences occur simultaneously, ie structures in which:
L ¹ , L ² , L ³ is the same or different at each occurrence selected from the above-mentioned groups according to the formulas (2) to (41), wherein a maximum of three symbols X in each group represent N;
Y is the same or different at each occurrence, a divalent group selected from CR ₂ or O;
n is the same or different at every occurrence 0, 1 or 2.

Particularly preferred structures according to formula (1) are structures in which:
L ¹ , L ² , L ³ is the same or different at each occurrence selected from the above-mentioned groups according to formulas (2), (7), (9), (10), (12), (13), (15 ), (33), (34), (37), (39), (40) or (41), wherein a maximum of two symbols X in each group are N;
Y is the same or different every occurrence CR ₂ ;
n is the same or different at every occurrence 0 or 1.

The other symbols and indices used have the meanings given above.

Preference is furthermore given to compounds of the formula (1) or of the abovementioned preferred embodiments in which R is identical or different on each occurrence for H, D, F, CN, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms, each of which may be substituted with one or more R ¹ radicals, wherein one or more non-adjacent CH ₂ groups is represented by R ¹ C = CR ¹ , O or S may be substituted and one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 18 aromatic ring atoms, each of which may be substituted by one or more R ¹ , or a Diarylaminogruppe 10 to 20 aromatic ring atoms, which may be substituted by one or more radicals R ¹ , or a combination of these systems; two or more substituents R may also together form a mono- or polycyclic aliphatic, aromatic and / or benzoannellated ring system. Particularly preferably, the symbol R in these compounds, identical or different at each occurrence, stands for H, D, F, a straight-chain alkyl group having 1 to 6 C atoms or a branched alkyl group having 3 to 6 C atoms, each with a or more radicals R ¹ may be substituted, wherein one or more H atoms may be replaced by F, or an aryl group having 6 to 10 aromatic ring atoms or an aromatic ring system having 12 to 18 aromatic ring atoms, each by one or more radicals R ¹ may be substituted; two or more substituents R may also together form a mono- or polycyclic aliphatic, aromatic and / or benzoannellated ring system.

Preference is furthermore given to compounds in which at least two of the partial ligands L ¹ , L ² and L ^{3 are} identical and are likewise substituted.

Examples of suitable ligands which coordinate to M as neutral or monoanionic ligands are the ligands listed below, wherein they are present in deprotonated form when coordinated as monoanionic ligands.

Examples of suitable ligands which coordinate to M as neutral, monoanionic or dianionic ligands are the ligands listed below, where, when coordinated as monoanionic ligands, they are present in each case in a single deprotonated form and in coordination as dianionic ligands in each case in completely deprotonated form.

Examples of suitable ligands which coordinate to M as neutral, monoanionic, dianionic or trianionic ligands are the ligands listed below, wherein in coordination as monoanionic ligands each in a single deprotonated form, in coordination as dianionic ligands in each case in two-deprotonated form and in coordination as trianionic ligands each in fully deprotonated form.

As described above, a ligand which balances the charge of the metal atom is preferably selected for the metal complexes, ie a monoanionic ligand for Cu, Ag and Au, a dianionic ligand for Zn and a trianionic ligand for Al. A in the structures listed above stands for N or P. The aromatics indicated by dashed bonds may or may not be present independently, but only if they form a complete aromatic group. Furthermore, individual C atoms in the ligands listed above may also be replaced by N. Furthermore, the structures may be substituted by one or more radicals R, where R has the abovementioned meanings. In the ligands shown above, these are given a three-digit number for the sake of clarity. Each of these three numbers indicates the ring size that forms the corresponding "arm" of the polypodal ligand with the metal atom.

Examples of compounds according to the invention of formula (1) are the compounds depicted below.

The synthesis of the ligands can in principle be carried out analogously for all ligands, in each case a tertiary amine or phosphine being synthesized. This can be done in different ways.

One possibility is the triple amination of ammonia, as shown in Scheme 1, generally below, for the synthesis of a tertiary amine with two different arms.

Scheme 1:

For this purpose, mono-protected ammonia is reacted with two equivalents of an aldehyde under reducing conditions, it being possible to use other protective groups instead of Boc. The amination can be analogous to A. Beni et al. (Chem. Eur. J. 2008, 14, 1804-1813) be performed. The reaction product is deprotected and reacted under reducing conditions with another aldehyde, which may be the same or different than the first aldehyde. Thus, the synthesis of a ligand with two equal arms and a different arm or three equal arms is possible. Similarly, using two different amine protecting groups with different cleavage conditions also allows the synthesis of ligands with three different arms.

Another possibility for the preparation of a secondary amine is, for example, the reaction of an ethene derivative with ammonium chloride, as shown generally in the following scheme ( Reaction analogous to K. Ladomenou et al., Tetrahedron 2007, 63, 2882-2887 ). This secondary amine can then be converted, for example analogously to the reaction shown in Scheme 1, further to the tertiary amine.

Scheme 2:

A possible synthesis of tertiary phosphines with two different arms is shown in Scheme 3 below.

Scheme 3:

Here, R 'or R' 'is, identically or differently on each occurrence, an alkyl, aryl or heteroaryl group as defined above for R, and X is Cl, Br or I.

The synthesis can be analogous to Tsurusaki et al., Bull. Chem. Soc. Jpn. 2010, 83 (5), 456-478 be performed. For this purpose, an aryl, heteroaryl or alkyl halide is lithiated and reacted with a doubly protected phosphine chloride, wherein instead of NEt ₂ , other protective groups can be used. The reaction product is deprotected to the corresponding phosphine dichloride and reacted with a Grignard reagent to form the tertiary phosphine. Thus, the synthesis of a ligand with two equal arms and a different arm or three equal arms is possible. Similarly, using two different phosphine protecting groups with different cleavage conditions, it is also possible to synthesize ligands with three different arms.

The complexes according to formula (1) or according to the above-mentioned preferred embodiments can be prepared in principle by various methods. In order to obtain a neutral metal complex, the level of charge of the ligand must balance the charge of the metal. The metal complex is reacted with the free ligand, optionally in deprotonated form.

In this case, the deprotonation of the ligand in situ by a metal precursor with a protonatable, preferably non-nucleophilic counterion such. As mesityl or amide done. This gives directly the neutral metal complex of the formula (1).

Alternatively, first the ligand can be deprotonated with a base and then reacted with a metal salt which replaces the cation of the deprotonated ligand. One then gets directly the neutral metal complex.

A third possibility is the reaction of a metal salt with the non-deprotonated ligand. This results in an intermediate charged positively charged metal complex, which can then be deprotonated to the neutral complex.

The synthesis of cryptates can be carried out, for example, by reacting a complex with a corresponding tripodal ligand with a bridging unit, as illustrated by an example in Scheme 4 below.

Scheme 4:

Another object of the present invention is thus a process for preparing the compounds of the invention, characterized by the reaction of a metal salt or metal complex of the metal M with the corresponding free ligand, optionally in deprotonated form. If the ligand is not used in deprotonated form, a deprotonation step can optionally be carried out subsequent to the complexation. In particular, metal salts or metal complexes with protonatable, non-nucleophilic counterion are used.

Examples of suitable copper compounds which can be used as starting materials are, in particular, copper (I) salts with weakly coordinating anions, such as Cu (OAc), Cu ₂ (CO ₃ ), [Cu (MeCN) ₄ ] [BF ₄ ], CuBF ₄ , [Cu (MeCN) ₄ ] [PF ₆ ], copper (I) mesityl or copper (I) amides, such as. B. copper (I) pyrrolidine. Examples of suitable silver compounds which can be used as starting materials are, in particular, silver (I) salts with weakly coordinating anions, such as Ag (OAc), Ag ₂ (CO ₃ ), [Ag (MeCN) ₄ ] [BF ₄ ], AgBF ₄ , [Ag (MeCN) ₄ ] [PF ₆ ], silver (I) mesityl or silver (I) amides, such as. For example, silver (I) pyrrolidine. Examples of suitable gold compounds which can be used as starting materials are [Au (PR ₃ ) (MeCN)] [SbF ₆ ], AuHal * SR _{2 ,} [Au (PR ₃ ) (N (SO ₂ ) ₂ (CF ₃ ) ₂ )] and gold (I) mesityl, where Hal is a halide and R is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 amino-atom ring atoms. Examples of suitable zinc compounds which can be used as starting materials are ZnMe ₂ , Zn (OAc) ₂ , [Zn (TMHD) ₂ ] (CAS: 14363-14-5) and [Zn (dibutyldithiocarbamate)]. Examples of suitable aluminum compounds which can be used as starting materials are AlMe ₃ , Al (OH) ₃ , Al (NO ₃ ) ₃ , Al ₂ (SO ₄ ) ₃ , Al (sec-butoxide) ₃ , Al (OAc) ₃ , AlPO ₄ , Al (acac) ₃ and Al (ethoxide) ₃ .

The synthesis can also be activated thermally, photochemically or by microwave radiation and / or be carried out in an autoclave or generally under pressure. By these methods, the complexes can be obtained in high purity, preferably in a purity of> 99% by ¹ H-NMR or HPLC.

For processing from solution, for example by spin coating or by printing processes, solutions or formulations of the compounds 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, 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, α-terpineol, benzothiazole, butylbenzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethylbenzoate, indane, methylbenzoate, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene , Dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis (3,4-dimethylphenyl ) ethane or mixtures of these solvents.

A further subject of the present invention is therefore a formulation containing a compound according to the invention and at least one further compound. The further compound may be, for example, one or more solvents, in particular one or more of the abovementioned solvents. How such solutions can be produced is known to the person skilled in the art and is described, for example, in US Pat WO 2002/072714 , of the WO 2003/019694 and the literature cited therein. However, 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 above-described compounds of the formula (1) or the above-mentioned preferred embodiments can be used in an electronic device as an active component. Another object of the present invention is therefore the use of a compound according to formula (1) or according to one of the preferred embodiments in an electronic device. Furthermore, the compounds according to the invention can be used for the production of singlet oxygen, in photocatalysis or in oxygen sensors.

Yet another object of the present invention is an electronic device containing at least one compound according to formula (1) or according to one of the preferred embodiments.

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 of the above-mentioned formula (1). Here, 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-lasers) in at least one layer at least one compound according to the above-mentioned formula (1). Particularly preferred are organic electroluminescent devices. 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. 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. Likewise, 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.

In this case, the organic electroluminescent device may contain an emitting layer, or it may contain a plurality of emitting layers. If several emission layers are present, they preferably have a total of a plurality of emission maxima between 380 nm and 750 nm, so that overall white emission results, ie in the emitting layers different emitting compounds are used, which can fluoresce or phosphoresce. A preferred embodiment is three-layer systems, wherein the three layers show blue, green and orange or red emission (see eg. WO 2005/011013 ) or systems which have more than three emitting layers. Another preferred embodiment is two-layer systems wherein the two layers show either blue and yellow or blue-green and orange emission. Two-layer systems are of particular interest for lighting applications. Such embodiments are particularly suitable with the compounds according to the invention, since they often show yellow or orange emission. The white-emitting electroluminescent devices can be used for lighting applications or as a backlight for displays or with color filters as a display.

In a preferred embodiment of the invention, the organic electroluminescent device contains the compound of the formula (1) or the preferred embodiments listed above as the emitting compound in one or more emitting layers. This is especially true when M is Cu, Ag or Au.

When the compound of the formula (1) is used as an 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 formula (1) and the matrix material contains between 1 and 99% by volume, preferably between 2 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 formula (1) based on the total mixture of emitter and matrix material. Accordingly, the mixture contains between 99 and 1% by volume, preferably between 98 and 10% by volume, more preferably between 97 and 60% by volume, in particular between 95 and 85% by volume of the matrix material or of the matrix materials to the total mixture of emitter and matrix material.

As matrix material, it is generally possible to use all materials known for this purpose according to the prior art. Preferably, 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 2004/013080 . WO 2004/093207 . WO 2006/005627 or WO 2010/006680 , Triarylamines, carbazole derivatives, e.g. B. CBP (N, N-Biscarbazolylbiphenyl), m-CBP or in WO 2005/039246 . US 2005/0069729 . JP 2004/288381 . EP 1205527 . WO 2008/086851 or US 2009/0134784 disclosed carbazole derivatives, indolocarbazole derivatives, e.g. B. according to WO 2007/063754 or WO 2008/056746 , Indenocarbazole derivatives, e.g. B. according to WO 2010/136109 or WO 2011/000455 , Azacarbazoles, e.g. B. according to EP 1617710 . EP 1617711 . EP 1731584 . JP 2005/347160 , bipolar matrix materials, e.g. B. according to WO 2007/137725 , Silane, z. B. according to WO 2005/111172 , Azaborole or Boronester, z. B. according to WO 2006/117052 , Diazasilolderivete, z. B. according to WO 2010/054729 , Diazaphospholderivate, z. B. according to WO 2010/054730 , Triazine derivatives, e.g. B. according to WO 2010/015306 . WO 2007/063754 or WO 2008/056746 , Zinc complexes, e.g. B. according to EP 652273 or WO 2009/062578 , Dibenzofuran derivatives, e.g. B. according to WO 2009/148015 , or bridged carbazole derivatives, e.g. B. according to US 2009/0136779 . WO 2010/050778 . WO 2011/042107 or WO 2011/088877 ,

It may also be preferred to use several different matrix materials as a mixture. Particularly suitable for this are mixtures of at least one electron-transporting matrix material and at least one hole-transporting matrix material or mixtures of at least two electron-transporting matrix materials or mixtures of at least one hole- or electron-transporting matrix material and at least one further material with a large band gap, which is thus largely electrically inert and not or not substantially participate in charge transport, such. In WO 2010/108579 described.

It is further preferred to use a mixture of two or more triplet emitters together with a matrix. The triplet emitter with the shorter-wave emission spectrum serves as a co-matrix for the triplet emitter with the longer-wave emission spectrum. Thus, for example, blue or green emitting triplet emitters can be used as a co-matrix for the compound according to the invention of the formula (1) if the compound of the formula (1) emits a longer wavelength. For the purposes of the present invention, all luminescent compounds of the formula (1) are to be regarded as triplet emitters.

Furthermore, it may be preferable to use the compound of the invention as a matrix material, in particular as a matrix material for triplet emitter. This is especially true when M stands for Zn.

Furthermore, it may be preferable to use the compound according to the invention as an electron transport material or as a hole blocking material. This is especially true when M stands for Al.

As the cathode are metals with low work function, metal alloys. or multilayer structures of various metals, such as alkaline earth metals, alkali metals, main group metals or lathanoids (eg, Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys of an alkali or alkaline earth metal and silver, for example an alloy of magnesium and silver. In multilayer structures, it is also possible, in addition to the metals mentioned, to use further metals which have a relatively high work function, such as, for example, B. Ag, which then usually combinations of metals, such as Ca / Ag or Ba / Ag are used. It 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, Li ₂ O, BaF ₂ , MgO, NaF, CsF, Cs ₂ CO ₃ , etc.). The layer thickness of this layer is preferably between 0.5 and 5 nm.

As the anode, high workfunction materials are preferred. Preferably, the anode has a work function greater than 4.5 eV. Vacuum up. On the one hand, metals with a high redox potential, such as Ag, Pt or Au, are suitable for this purpose. On the other hand, metal / metal oxide electrons (for example Al / Ni / NiO _x , Al / PtO _x ) may also be preferred. For some applications, at least one of the electrodes must be transparent to either to allow the irradiation of the organic material (O-SC) or the extraction of light (OLED / PLED, O-LASER). A preferred construction uses a transparent anode. Preferred anode materials here are conductive mixed metal oxides. Particularly preferred are indium tin oxide (ITO) or indium zinc oxide (IZO). Preference is furthermore given to conductive, doped organic materials, in particular conductive doped polymers.

In the further layers, it is generally possible to use all materials as used in the prior art for the layers, and the person skilled in the art can combine any of these materials in an electronic device with the inventive materials without inventive step.

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.

Further preferred is an organic electroluminescent device, characterized in that one or more layers are coated with a sublimation process. The materials are vapor-deposited in vacuum sublimation systems at an initial pressure of usually less than 10 ^-5 mbar, preferably less than 10 ^-6 mbar. It is also possible that the initial pressure is even lower, for example less than 10 ^-7 mbar.

Also preferred is 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. A special case of this process is the OVJP (Organic Vapor Jet Printing) process, in which the materials are applied directly through a nozzle and thus structured (eg. MS Arnold et al., Appl. Phys. Lett. 2008, 92, 053301 ).

Further preferred is an organic electroluminescent device, characterized in that one or more layers of solution, such. B. by spin coating, or with any printing process, such. B. screen printing, flexographic printing or offset printing, but particularly preferably LITI (Light Induced Thermal Imaging, thermal transfer printing) or ink-jet printing (ink jet printing) can be produced. For this purpose, soluble compounds are necessary, which are obtained for example by suitable substitution.

The organic electroluminescent device may also be fabricated as a hybrid system by applying one or more layers of solution and depositing one or more other layers. Thus, for example, it is possible to apply an emitting layer containing a compound of formula (1) and a solution matrix material and then vacuum evaporate a hole blocking layer and / or an electron transport layer.

These methods are generally known to the person skilled in the art and can be applied by him without problems to organic electroluminescent devices containing compounds of the formula (1) or the preferred embodiments listed above.

• 1. Im Gegensatz zu vielen Metallkomplexen gemäß dem Stand der Technik, die der teilweisen oder vollständigen pyrolytischen Zersetzung bei Sublimation unterliegen, weisen die erfindungsgemäßen Verbindungen eine hohe thermische Stabilität auf. Insbesondere die neutralen Verbindungen gemäß der vorliegenden Erfindung weisen dabei eine überraschend niedrige Sublimationstemperatur auf.
• 2. Organische Elektrolumineszenzvorrichtungen enthaltend die erfindungsgemäßen Verbindungen als emittierende Materialien, als Matrixmaterialien oder als Elektronentransportmaterialien weisen weiten gute Eigenschaften in Bezug auf Effizienz, Betriebsspannung und Lebensdauer auf.
• 3. Die Verbindungen gemäß Formel (1) basieren nicht auf den seltenen Metallen Iridium oder Platin, was zur Ressourcenschonung dieser Metalle beiträgt.
• 4. Die Komplexe gemäß Formel (1) bzw. gemäß der oben aufgeführten bevorzugten Ausführungsformen sind gut und in hohen Ausbeuten und hohen Reinheiten synthetisch zugänglich.

The electronic devices according to the invention, in particular organic electroluminescent devices, are distinguished by the following surprising advantages over the prior art:

• 1. Unlike many prior art metal complexes which undergo partial or complete pyrolytic decomposition on sublimation, the compounds of the present invention have high thermal stability. In particular, the neutral compounds according to the present invention have a surprisingly low sublimation temperature.
• 2. Organic electroluminescent devices comprising the compounds according to the invention as emissive materials, as matrix materials or as electron-transport materials have wide good properties in terms of efficiency, operating voltage and service life.
• 3. The compounds according to formula (1) are not based on the rare metals iridium or platinum, which contributes to the conservation of resources of these metals.
• 4. The complexes according to formula (1) or according to the above-mentioned preferred embodiments are well and synthetically accessible in high yields and high purities.

The above advantages are not accompanied by a deterioration of the other electronic properties.

The invention is explained in more detail by the following examples without wishing to restrict them thereby. The person skilled in the art can prepare further complexes according to the invention from the descriptions without inventive step and use them in organic electronic devices or use the method according to the invention and thus carry out the invention throughout the claimed range.

Description of the figures:

1 : Crystal structure of [Cu (InPEA)] (BF ₄ ), showing the distorted tetrahedral coordination of the ligand to the Cu (the protons and the BF ₄ anion are not shown for clarity).

2 : Absorption and emission spectrum of [Cu (InPEA)] (BF ₄ ) in the solid (pure substance, emission maximum: 519 nm, yellow-green emission).

3 : Absorption and emission spectrum of [Cu (InPEA)] (BF ₄ ) in solution in dichloromethane (emission maximum: 464 nm, blue emission).

4 : Absorption and emission spectrum of [Cu (InPEA)] in solution in dichloromethane (emission maximum: 506 nm, yellow-green emission).

5 : Crystal structure of [Cu (OPEA)] (BF ₄ ), showing the distorted tetrahedral coordination of the ligand to the Cu (the protons and the BF ₄ anion are not shown for clarity).

6 : Absorption and emission spectrum of [Cu (OPEA)] (BF ₄ ) in the solid (pure substance, emission maximum: 525 nm, yellow-green emission).

Examples:

Unless stated otherwise, the following syntheses are carried out under an inert gas atmosphere in dried solvents. The solvents and reagents can be purchased from ALDRICH or ABCR.

Example 1: Synthesis of ligand InPEA (N - ((1H-indol-7-yl) methyl) -2- (pyridin-2-yl) -N- (2- (pyridin-2-yl) ethyl) ethanamine)

Step 1:

In a 250 ml Schlenk flask, 1.25 g of bis (2- (pyridin-2-yl) ethyl) amine (5.51 mmol) (synthesized according to K. Ladomenou et al., Tetrahedron 2007, 63, 2882-2887 ) and 1.35 g of N-Boc-indole-7-carbaldehyde (CAS: 597544-14-4) (5.51 mmol) and then dissolved in 30 ml of dichloromethane. Subsequently, an inert suspension of 1.63 g of Na triacetoxyborohydride (7.71 mmol) in 30 ml DCM is added. The reaction mixture is stirred at RT for 18 h. Then 80 ml of saturated NaHCO ₃ solution are added and again for 30 min touched. It is then extracted three times with dichloromethane, dried over MgSO ₄ and concentrated in vacuo. Further purification of the resulting orange oil does not occur; it will continue to be used directly.

Step 2:

In a 30 ml pressure vessel, the synthesized product from step 1 is dissolved in 4 ml of THF under an inert gas atmosphere, and then 16 ml of NaOMe solution (0.57 M in MeOH) are added. The vessel is sealed pressure-tight and stirred in a microwave at 150 ° C for 3 h. The pressure increases continuously to 27 bar. After the pressure remains constant, it is cooled to room temperature, the reaction mixture is poured into 60 ml H ₂ O, then extracted three times with 30 ml portions of ether, dried over MgSO ₄ and concentrated in vacuo. The purification is carried out in a short silica gel column (pure ethyl acetate, R _f = 0.04). The product is a colorless solid. Yield 58%.
¹ H NMR (DCM-d ₂ , 400.13 MHz): δ 10.70 (bs, 1H), 8.39 (m, 2H), 7.52 (m, 1H), 7.48 (m, 2H), 7.09-7.11 (m, 1H) , 7.06 (m, 2H), 6.97 (m, 2H), 6.90 (m, 2H), 6.44 (m, 1H), 3.98 (s, 2H), 2.82-2.86 (s, 8H).
¹³ C NMR (DCM-d ₂ , 100.13 MHz): δ 161.49, 149.35, 136.72, 135.93, 128.55, 124.89, 123.58, 123.06, 121.82, 121.54, 119.97, 119.30, 101.55, 58.04, 54.62, 36.00.

Example 2: Synthesis of [Cu (InPEA)] [BF ₄ ]

204.0 mg (0.57 mmol) of InPEA from Example 1 and 180.0 mg (0.57 mmol) of [Cu (MeCN) ₄ ] [BF ₄ ] are rendered inert in a Schlenk flask, dissolved in 30 ml of THF and heated for 2 h stirred at room temperature. The result is a yellow-brown suspension. This is filtered and diethyl ether allowed to diffuse. This produces yellow crystals.
¹ H NMR (DCM-d ₂ , 400.13 MHz): δ 9.33 (bs, 1H), 8.17 (m, 2H), 7.73 (m, 2H), 7.34 (m, 1H), 7.32 (m, 1H), 7.24 (m, 2H), 7.17-7.21 (m, 2H), 7.00 (m, 1H), 7.86 (m, 1H), 6.50 (m, 1H), 4.01 (s, 2H), 3.05-3.27 (m, 8H ).
¹³ C { ¹ H} NMR (DCM-d ₂ , 100.13 MHz): δ 160.67, 150.44, 146.34, 139.34, 130.01, 127.17, 125.92, 123.51, 123.33, 121.39, 120.56, 120.18, 104.64, 56.51, 54.47, 36.22.

The [Cu (InPEA)] [BF ₄ ] salt may e.g. B. with potassium tert-butoxide (KOtBu) are deprotonated. The product [Cu (InPEA)], ie the neutral complex, can be clearly detected by the ¹ H NMR spectrum.

Example 3: Synthesis of [Cu (InPEA)]

191.1 mg (0.54 mmol) of InPEA from Example 1 and 98.0 mg (0.54 mmol) of Cu mesityl are dissolved in 4 ml of toluene in a glove box and stirred for 1 h at room temperature. The result is an orange solution. This is filtered and the solvent removed in vacuo. The pure complex is obtained by sublimation at 1 × 10 ^-2 mbar and 180 ° C.
¹ H NMR (DCM-d ₂ , 400.13 MHz): δ 8.40 (m, 2H), 7.60 (m, 2H), 7.49 (m, 1H), 7.42-7.45 (m, 1H), 7.13 (m, 2H) , 7.06 (m, 2H), 6.77-6.82 (m, 2H), 6.44 (m, 1H), 4.10-4.34 (m, 2H), 2.68-2.99 (m, 8H).

Example 4: Synthesis of ligand InPA (N - ((1H-indol-7-yl) methyl) -1- (pyridin-2-yl) -N- (pyridin-2-ylmethyl) methanamine)

Step 1:

In a 250 ml Schlenk flask, 1.02 g of di (2-picolyl) amine (CAS: 1539-42-0) (5.14 mmol) and 1.26 g of N-Boc-indole-7-carbaldehyde (CAS: 597544 -14-4) (5.14 mmol) and then dissolved in 30 ml of dichloromethane. Subsequently, an inert suspension of 1.52 g of Na triacetoxyborohydride (7.19 mmol) in 40 ml of dichloromethane is added. The reaction mixture is stirred for 18 h at room temperature. Thereafter, 70 ml of saturated NaHCO ₃ solution are added and the mixture is stirred for a further 30 min. It is then extracted three times with dichloromethane, dried over MgSO ₄ and concentrated in vacuo. Further purification of the resulting orange oil does not occur. Yield 99%.
¹ H NMR (DCM-d ₂ , 400.13 MHz): δ 8.57 (m, 2H), 7.58-7.67 (m, 4H), 7.48-7.53 (m, 3H), 7.27 (m, 1H), 7.11 (m, 2H), 6.63 (m, 1H), 4.39 (s, 2H), 3.85 (s, 4H), 1.65 (s, 9H).
¹³ C NMR (DCM-d ₂ , 100.13 MHz): δ 159.76, 149.98, 149.27, 136.28, 134.43, 132.55, 128.75, 127.42, 126.45, 123.56, 123.36, 122.11, 120.45, 107.47, 83.67, 58.99, 58.92, 28.35.

Step 2:

2.19 g of Boc-InPA (5.11 mmol) from step 1 are dissolved in 8 ml of THF in a 30 ml pressure vessel under an inert gas atmosphere and then 12 ml of NaOMe solution (0.57 M in MeOH) are added. The vessel is sealed pressure-tight and stirred in a microwave at 130 ° C for 2 h. The pressure increases continuously to 27 bar. After the pressure remains constant, it is cooled to room temperature, the reaction mixture is poured into 60 ml of H ₂ O, then extracted three times with 30 ml of ether, dried over MgSO ₄ and concentrated in vacuo. The purification is carried out with a silica gel column (pure ethyl acetate, R _f = 0.28). The product is a colorless solid. Yield 63%.
¹ H NMR (DCM-d ₂ , 400.13 MHz): δ 12.55 (bs, 1H), 8.66 (m, 2H), 7.67 (m, 1H), 7.59 (m, 2H), 7.55-7.57 (m, 1H) , 7.29 (m, 2H), 7.08-7.18 (m, 4H), 6.63-6.67 (m, 1H), 4.01 (s, 2H), 3.95 (s, 4H).
¹³ C NMR (DCM-d ₂ , 100.13 MHz): δ 160.08, 149.40, 136.98, 136.41, 128.69, 124.86, 123.73, 123.15, 122.52, 121.97, 120.26, 119.26, 101.57, 60.11, 57.65.
Elemental analysis: Calculated (%) for C ₂₁ H ₂₀ N ₄ (328.41 g / mol): C, 76.80; H, 6.14; N, 17.06; found: C, 76.44; H, 6.09; N, 17.02.

Example 5: Synthesis of ligand PBPA (N- (2- (1H-pyrrol-2-yl) benzyl) -1- (pyridin-2-yl) -N- (pyridin-2-ylmethyl) methanamine)

Step 1:

In a 250 ml Schlenk flask, 868.1 mg of di (2-picolyl) amine (4.36 mmol) and 1.182 g of tert-butyl 2- (2-formylphenyl) -1H-pyrrole-1-carboxylate (CAS: 445262- 65-7) (4.36 mmol) and then dissolved in 20 ml of dichloromethane. Subsequently, an inert suspension of 1.239 g of sodium tetoxyborohydride (6.10 mmol) in 30 ml of dichloromethane is added. The reaction mixture is stirred for 18 h at room temperature. Then 60 ml of saturated NaHCO ₃ solution are added and the mixture is stirred for a further 30 min. It is then extracted three times with dichloromethane, dried over MgSO ₄ and concentrated in vacuo. Further purification of the resulting orange oil does not occur. Yield 95%.
¹ H NMR (DCM-d ₂ , 250.13 MHz): δ 8.51 (m, 2H), 7.94 (m, 1H), 7.58-7.71 (m, 5H), 7.46 (m, 1H), 7.25-7.28 (m, 1H), 7.07-7.17 (m, 3H), 6.32 (m, 1H), 6.15 (m, 1H), 3.52-3.85 (m, 6H), 1.20 (s, 9H).
¹³ C NMR (DCM-d ₂ , 62.90 MHz): δ 160.38, 149.47, 149.37, 139.75, 136.70, 135.28, 133.21, 131.05, 128.56, 128.40, 126.52, 122.99, 122.29, 121.94, 114.73, 110.95, 83.60, 60.77, 56.21, 27.70.

Step 2:

1.2 g of Boc-PBPA (2.64 mmol) from step 1 are dissolved in 8 ml of THF in a 30 ml pressure vessel under an inert gas atmosphere and then 12 ml of NaOMe solution (0.57 M in MeOH) are added. The vessel is sealed pressure-tight and stirred in a microwave at 150 ° C for 3 h. The pressure increases continuously to 23 bar. It is then cooled to room temperature, the reaction mixture is added to 60 ml of H ₂ O, then extracted three times with 30 ml of ether, dried over MgSO ₄ and concentrated in vacuo. The purification is carried out on a silica gel column (pure ethyl acetate, R _f = 0.28). The product is a colorless oil. Yield 71%.
¹ H NMR (DCM-d ₂ , 400.13 MHz): δ 12.89 (bs, 1H), 8.59 (m, 2H), 7.66 (m, 1H), 7.55 (m, 2H), 7.39 (m, 1H), 7.33 (m, 1H), 7.22 (m, 2H), 7.17 (m, 1H), 7.10-7.14 (m, 2H), 6.99-7.02 (m, 1H), 6.46-6.49 (m, 1H), 6.27-6.30 (m, 1H), 3.93 (s, 2H), 3.92 (s, 4H).
¹³ C NMR (DCM-d ₂ , 100.13 MHz): δ 158.81, 149.84, 136.61, 135.45, 134.04, 132.81, 132.66, 129.07, 128.83, 126.02, 124.19, 122.54, 120.20, 109.05, 107.88, 61.06, 60.30.

Example 6: Synthesis of the ligand OPEA (2 - ((bis (2- (pyridin-2-yl) ethyl) amino) methyl) phenol)

2.40 g of bis (2- (pyridin-2-yl) ethyl) amine (10 mmol) and 1.29 g of salicylaldehyde (10 mmol) are rendered inert in a 250 ml Schlenk flask and then dissolved in 80 ml of dichloromethane. Subsequently, an inert suspension of 3.13 g of sodium triacetoxyborohydride (15 mmol) in 80 ml of dichloromethane is added. The reaction mixture is stirred for 18 h at room temperature. Thereafter, 160 ml of saturated NaHCO ₃ solution are added and the mixture is stirred for a further 30 min. It is then extracted three times with dichloromethane, dried over MgSO ₄ and concentrated in vacuo. The resulting yellow oil is purified on a 7 cm silica gel column (pure ethyl acetate, R _f = 0.08). Yield 84%.
¹ H NMR (DCM-d ₂ , 400.13 MHz): δ 10.21 (bs, 1H), 8.53 (m, 2H), 7.54 (m, 2H), 7.16 (m, 1H), 7.05-7.11 (m, 4H) , 7.03 (m, 1H), 6.76-6.83 (m, 2H), 3.87 (s, 2H), 2.97-3.10 (s, 8H).
¹³ C NMR (DCM-d ₂ , 100.13 MHz): δ 160.00, 158.45, 149.62, 136.65, 129.19, 128.99, 123.58, 122.78, 121.67, 119.31, 116.33, 58.04, 53.34, 35.09.

Example 7: Synthesis of [Cu (OPEA)] (BF ₄ )

333.3 mg (1 mmol) of OPEA from Example 6 and 314.6 mg (1 mmol) of [Cu (MeCN) ₄ ] [BF ₄ ] are rendered inert in a Schlenk flask, dissolved in 40 ml of THF and stirred at room temperature for 2 h. The result is a yellow solution. This is filtered and overlaid with n-hexane. This produces yellow crystals. Yield: 91%.
¹ H NMR (DCM-d ₂ , 400.13 MHz): δ 8.80 (m, 2H), 8.46 (bs, 1H), 7.69 (m, 2H), 7.28 (m, 2H), 7.18 (m, 2H), 6.96 (m, 1H), 6.89 (m, 1H), 6.85 (m, 1H), 6.61 (m, 1H), 3.66 (s, 2H), 2.80-3.18 (m, 8H). ¹³ C { ¹ H} NMR (DCM-d ₂ , 100.13 MHz): δ 160.18, 155.01, 151.65, 138.52, 132.48, 130.28, 125.18, 123.67, 122.34, 120.51, 116.38, 57.22, 55.98, 36.10.
Elemental analysis calculated (%) for C ₂₁ H ₂₃ N ₃ O ₄ BCuF (483.78 g / mol): C, 52.14; H, 4.79; N, 8.69. Found: C, 52.05; H, 4.64; N, 8.67.

Example: Production of the OLEDs

1) Vacuum Processed Devices:

The preparation of inventive OLEDs and OLEDs according to the prior art is carried out according to a general method according to WO 2004/058911 , which is adapted to the conditions described here (layer thickness variation, materials used).

The following examples introduce the results of different OLEDs. Glass slides with structured ITO (50 nm, indium tin oxide) form the substrates to which the OLEDs are applied. The OLEDs have in principle the following layer structure: substrate / hole transport layer 1 (HTL1) consisting of HTM doped with 3% NDP-9 (commercially available from Novaled), 20 nm / hole transport layer 2 (HTL2) / optional electron blocker layer (EBL) / emission layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL) and finally a cathode. The cathode is formed by a 100 nm thick aluminum layer.

First, vacuum-processed OLEDs will be described. For this purpose, all materials are thermally evaporated in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material, host material) and an emitting dopant (dopant, emitter), which is admixed to the matrix material or the matrix materials by co-evaporation in a specific volume fraction. An indication such as M1: M2: [Cu (InPEA)] (55%: 35%: 10%) here means that the material M1 in a volume fraction of 55%, M2 in a proportion of 35% and [Cu (InPEA) ] is present in a proportion of 10% in the layer. Analogously, 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. For this purpose, 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 characteristic curves (IUL characteristic curves).

Use of compounds according to the invention as emitter materials in OLEDs

The compounds according to the invention can be used inter alia as emitter materials in the emission layer in OLEDs. Table 1: Structure of the OLED Ex. HTL2 thickness EBL thickness EML thickness HBL thickness ETL thickness Red OLEDs D1 HTM 230 nm --- M1: M2: [Cu (InPEA)] (65%: 30%: 5%) 35 nm --- ETM1: ETM2 (50%: 50%) 40 nm D2 HTM 230 nm --- M1: M2: [Cu (InPEA)] (60%: 30%: 10%) 35 nm --- ETM1: ETM2 (50%: 50%) 40 nm D3 HTM 220 mn 10 nm M1: M2: [Cu (InPEA)] (65%: 30%: 5%) 35 nm --- ETM1: ETM2 (50%: 50%) 40 nm Table 2: Results of the vacuum-processed OLEDs Ex. EQE (%) 1000 cd / m ² Voltage (V) 1000 cd / m ² CIE x / y 1000 cd / m ² D1 9.4 3.9 0.51 / 12:40 D2 11.7 3.7 0.51 / 12:41 D3 17.2 4.2 0.49 / 12:43

2) Solution-processed devices made of soluble functional materials

The complexes according to the invention can also be processed from solution and lead there to process technology 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 (for example in US Pat WO 2004/037887 ). The structure is composed of substrate / ITO / PEDOT (80 nm) / interlayer (80 nm) / emission layer (80 nm) / cathode. For this purpose, substrates from Technoprint (Sodalimeglas) are used, to which the ITO structure (indium tin oxide, a transparent, conductive anode) is applied. 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. Thereafter, an 80 nm layer of PEDOT (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). To remove residual water from the layer, 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. Alternatively, the interlayer 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. To produce the emission layer, the emitters according to the invention are dissolved together with the matrix materials in toluene or THF. 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 80 nm is to be achieved by spin coating. The solution-processed devices contain an emission layer of (polystyrene): M3: M4: emitter (25%: 25%: 40%: 10%).

The emission layer is spin-coated in an inert gas atmosphere, in this case argon, and baked at 130 ° C. for 30 minutes. Finally, a cathode of barium (5 nm) and then aluminum (100 nm) (high-purity metals from Aldrich, especially barium 99.99% (Order No. 474711), Lesker vapor deposition units, typical vapor deposition pressure 5 × 10 ^-6 mbar) are vapor-deposited , Optionally, first a lock blocking layer and then an electron transport layer and then only the cathode (eg Al or LiF / Al) can be evaporated in vacuo. To protect the device from air and humidity, the device is finally encapsulated and then characterized. The above-mentioned OLED examples are not yet optimized, Table 3 summarizes the data obtained. Table 3: Results with solution processed materials Ex. emitter EQE (%) 1000 cd / m ² Voltage (V) 1000 cd / m ² CIE x / y 1000 cd / m ² Sol-D1 [Cu (INPEA)] 8.8 4.9 0.51 / 12:40 Sol-D2 [Cu (InPEA)] [BF ₄ ] 6.7 5.7 0:52 / 0.28 Sol-D3 [Cu (OPEA)] [BF ₄ ] 7.0 5.5 0.55 / 12:38

Table 4: Structural formulas of the materials used

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

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Claims (14)

Compound according to formula (1),

where the symbols and indices used are: M is selected from Cu, Ag, Au, Zn or Al; A is selected from N or P; Y is the same or different on each occurrence and is a divalent radical selected from CR ₂ , O, S, 1,2-vinylene, 1,2- or 1,3-phenylene or an ortho-linked heteroarylene group having 5 or 6 aromatic ring atoms, these groups may each be substituted by one or more radicals R; L ¹ , L ² , L ³ is the same or different each occurrence of a heteroaryl group having 5 to 25 aromatic ring atoms, which may be substituted by one or more radicals R and which contains a nitrogen, sulfur or oxygen atom, which coordinate to M may, or an aryl or heteroaryl group having 5 to 18 aromatic ring atoms, which may be substituted by one or more radicals R and which has an exocyclic donor atom selected from N, O, S or P, which coordinates to M and which by one or more radicals R may be substituted; while the partial ligands L ¹ , L ² and L ^{3 can} also be connected to one another via radicals R, which are bridged with one another; n is identical or different 0, 1, 2, 3, 4 or 5 at each occurrence; R is the same or different H, D, F, Cl, Br, I, N (R ¹ ) ₂ , CN, NO ₂ , OR ¹ , Si (R ¹ ) ₃ , B (OR ¹ ) ₂ , C at each occurrence (= O) R ¹ , P (= O) (R ¹ ) ₂ , S (= O) R ¹ , S (= O) ₂ R ¹ , OSO ₂ R ¹ , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which is substituted by one or more radicals R ¹ wherein one or more non-adjacent CH ₂ groups can be represented by R ¹ C =CR ¹ , C≡C, Si (R ¹ ) ₂ , C =O, C =S, C =NR ¹ , P (= O) ( R ¹ ), SO, SO ₂ , NR ¹ , O, S or CONR ¹ may be replaced and wherein one or more H atoms may be replaced by F, Cl, Br, I, CN or NO ₂ , or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ , or an aryloxy, heteroaryloxy, aralkyl or Heteroaralkylgr uppe with 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R ¹ , or a Diarylaminogruppe, Diheteroarylaminogruppe or Arylheteroarylaminogruppe having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R ¹ ; two or more substituents R may also together form a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and / or benzoannellated ring system; R ¹ is the same or different at each occurrence as H, D, F, Cl, Br, I, N (R ² ) ₂ , CN, NO ₂ , OH, Si (R ² ) ₃ , B (OR ₂ ) ₂ , C (= O) R ² , P (= O) (R ² ) ₂ , S (= O) R ² , S (= O) ₂ R ² , OSO ₂ R ² , a straight-chain alkyl, alkoxy or thioalkoxy group with 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more radicals R ² where one or more non-adjacent CH ₂ groups can be replaced by R ² C =CR ² , C≡C, Si (R ² ) ₂ , C =O, C =S, C =NR ² , P (OO) ( R ² ), SO, SO ₂ , NR ² , O, S or CONR ² may be replaced and wherein one or more H atoms may be replaced by F, Cl, Br, I, CN or NO ₂ , or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each of which may be substituted by one or more radicals R ² , or an aryloxy, heteroaryloxy, aralkyl or Heteroaralkylgru ppe having from 5 to 60 aromatic ring atoms which may be substituted by one or more radicals R ² , or a diarylamino group, diheteroarylamino group or arylheteroarylamino group having from 10 to 40 aromatic ring atoms which may be substituted by one or more radicals R ² ; two or more substituents R ^{1 may} also together form a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and / or benzoannellated ring system; R ² is the same or different at each occurrence H, D, F or an aliphatic, aromatic and / or heteroaromatic hydrocarbon radical having 1 to 20 C-atoms, in which also one or more H atoms by F can be replaced; two or more substituents R ^{2 may} also together form a mono- or polycyclic aliphatic, aromatic, heteroaromatic and / or benzoannellated ring system; in this case, the compound contains, if it is a charged compound, one or more counterions, which may be the same or different. Compound according to Claim 1, characterized in that M is Cu (I). A compound according to claim 1 or 2, characterized in that the compound is electrically neutral. Compound according to one or more of Claims 1 to 3, characterized in that the cycle which is formed from A, Y, M and L ¹ or L ² or L ³ comprises 5, 6, 7, 8 or 9 ring atoms, preferably 5, 6, 7 or 8 ring atoms and more preferably 5, 6 or 7 ring atoms. A compound according to one or more of claims 1 to 4, characterized in that L ¹ or L ² or L ^{3 has} 5 to 14 aromatic ring atoms, preferably 5 to 13 aromatic ring atoms and particularly preferably 5 to 10 aromatic ring atoms, wherein the aryl - or heteroaryl groups may be substituted by one or more radicals R. Compound according to one or more of claims 1 to 5, characterized in that L ¹ , L ² and L ^{3 are the} same or different at each occurrence selected from the groups of the formulas (2) to (41):

wherein R has the same meaning as described in claim 1, the groups coordinate to the metal M via the position indicated by *, the position indicated by # indicates the position at which the partial ligands L ¹ and L ² or L ³ to Y and / or A, and furthermore: X stands for each occurrence identically or differently for CR or N; D is the same or different at each occurrence and represents OH, O ^- , SH, S ^- , NR ₂ , NR ^- , PR ^- , PR ₂ , OR, SR, COO ^- , --C (= O) R, --CR (= NR) or -N (= CR ₂ ). Compound according to one or more of Claims 1 to 6, characterized in that Y, the same or different at each occurrence, is a divalent group selected from CR ₂ or O, more preferably CR ₂ , with the proviso that Y is not O, if A = N is. Compound according to one or more of Claims 1 to 7, characterized in that the following applies to the symbols and indices used: L ¹ , L ² , L ³ is the same or different at each occurrence and is selected from the abovementioned groups according to the formulas (2) to (41), wherein a maximum of three symbols X in each group stand for N; Y is the same or different at each occurrence, a divalent group selected from CR ₂ or O; n is the same or different at each occurrence 0, 1 or 2; and the other symbols and indices used have the meanings given in claims 1 and 6. Compound according to one or more of claims 1 to 8, characterized in that at least two of the partial ligands L ¹ , L ² and L ^{3 are the} same and are substituted equally. Process for the preparation of a compound according to one or more of Claims 1 to 9, characterized by the reaction of a metal salt or metal complex of the metal M with the corresponding free ligand, optionally in deprotonated form, optionally followed by a deprotonation step. Formulation containing at least one compound according to one or more of claims 1 to 9 and at least one further compound, in particular a solvent. Use of a compound according to one or more of claims 1 to 9 in an electronic device, for the production of singlet oxygen, in photocatalysis or in oxygen sensors. Electronic device, in particular selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical Cells or organic laser diodes, containing in at least one layer at least one compound according to one or more of claims 1 to 9. Electronic device according to claim 13, which is an organic electroluminescent device, characterized in that the compound according to one or more of claims 1 to 9 is contained in an emitting layer as an emitter or as a matrix or in a hole blocking layer or in an electron transport layer.

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