DE102015016016A1 - metal complexes - Google Patents

Abstract

The present invention relates to metal complexes and electronic devices, in particular organic electroluminescent devices containing these metal complexes.

Description

The present invention relates to metal complexes which are suitable for use, in particular as emitters, in organic electroluminescent devices.

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. Here are often used as the emitting materials organometallic complexes that show phosphorescence instead of fluorescence. For quantum mechanical reasons, up to four times energy and power efficiency is possible using organometallic compounds as phosphorescence emitters. According to the state of the art, iridium and platinum complexes are used in phosphorescent OLEDs as triplet emitters in particular. However, due to the rarity of the metals iridium and platinum, it would be desirable to conserve resources by having metal complexes with other metals that can be used as emitters in OLEDs.

The object of the present invention is therefore to provide new metal complexes which are suitable as emitters for use in OLEDs. In particular, the object is to provide emitters which do not require the use of iridium and platinum as metals and which exhibit good properties in terms of efficiency, operating voltage, lifetime, color coordinates, sublimability and / or solubility.

Surprisingly, it has been found that the copper chelate complexes described in more detail below achieve this object and are very well suited for use in an organic electroluminescent device. The complexes of the invention are thermally stable and have a low molecular weight, which has a positive effect on the sublimability of the compounds both in the purification and in the production of organic electroluminescent devices from the gas phase. These metal complexes and organic electroluminescent devices containing these complexes are therefore the subject of the present invention.

wobei für die verwendeten Symbole und Indizes gilt:
Cu ist Kupfer in der Oxidationsstufe +1;
X ist ein neutrales Stickstoffatom, NR³, O oder S;
A ist, wenn X für ein neutrales Stickstoffatom steht, bei jedem Auftreten gleich oder verschieden CR³ oder N und außerdem steht genau ein A für CR³=CR³, NR³, O oder S; und ist, wenn X für NR³, O oder S steht, bei jedem Auftreten gleich oder verschieden CR³ oder N, mit der Maßgabe, dass maximal zwei A für N stehen;
R¹ ist bei jedem Auftreten gleich oder verschieden H, D, F, Cl, Br, I, N(R³)₂, OR³, CN, COOR³, C(=O)N(R³)₂, Si(R³)₃, B(OR³)₂, C(=O)R³, P(=O)(R³)₂, S(=O)R³, S(=O)₂R³, OSO₂R³, eine geradkettige Alkylgruppe mit 1 bis 20 C-Atomen oder eine Alkenyl- oder Alkinylgruppe mit 2 bis 20 C-Atomen oder eine verzweigte oder cyclische Alkylgruppe mit 3 bis 20 C-Atomen, wobei die Alkyl-, Alkenyl- bzw. Alkinylgruppe jeweils mit einem oder mehreren Resten R³ substituiert sein kann und wobei eine oder mehrere nicht benachbarte CH₂-Gruppen durch Si(R²)₂, C=O, NR², O, S oder CONR² ersetzt sein können, oder ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 40 aromatischen Ringatomen, das jeweils durch einen oder mehrere Reste R³ substituiert sein kann; dabei können die beiden Reste R¹ auch miteinander ein mono- oder polycyclisches, aliphatisches, aromatisches oder heteroaromatisches Ringsystem bilden;
oder die beiden Reste R¹ stellen zusammen mit den Kohlenstoffatomen, an die sie gebunden sind, eine Gruppe der folgenden Formel (3) dar,

wobei W gleich oder verschieden bei jedem Auftreten für CR³ oder N steht, mit der Maßgabe, dass maximal zwei W für N stehen, und die beiden gestrichelten Bindungen die Verknüpfung mit dem Stickstoffatom bzw. der Heteroarylgruppe im Liganden darstellt;
R² ist bei jedem Auftreten gleich oder verschieden eine geradkettige Alkylgruppe mit 1 bis 20 C-Atomen oder eine Alkenyl- oder Alkinylgruppe mit 2 bis 20 C-Atomen oder eine verzweigte oder cyclische Alkylgruppe mit 3 bis 20 C-Atomen, wobei die Alkyl-, Alkenyl- oder Alkinylgruppe jeweils mit einem oder mehreren Resten R³ substituiert sein kann und wobei eine oder mehrere nicht benachbarte CH₂-Gruppen durch Si(R³)₂, C=O, NR³, O, S oder CONR³ ersetzt sein können, oder ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 40 aromatischen Ringatomen, das jeweils durch einen oder mehrere Reste R³ substituiert sein kann;
R³ ist bei jedem Auftreten gleich oder verschieden H, D, F, Cl, Br, I, N(R⁴)₂, OR⁴, CN, Si(R⁴)₃, B(OR⁴)₂, C(=O)R⁴, P(=O)(R⁴)₂, S(=O)R⁴, S(=O)₂R⁴, OSO₂R⁴, eine geradkettige Alkylgruppe mit 1 bis 20 C-Atomen oder eine Alkenyl- oder Alkinylgruppe mit 2 bis 20 C-Atomen oder eine verzweigte oder cyclische Alkylgruppe mit 3 bis 20 C-Atomen, wobei die Alkyl-, Alkenyl- oder Alkinylgruppe jeweils mit einem oder mehreren Resten R⁴ substituiert sein kann und wobei eine oder mehrere nicht benachbarte CH₂-Gruppen durch Si(R⁴)₂, C=O, NR⁴, O, S oder CONR⁴ ersetzt sein können, oder ein aromatisches oder heteroaromatisches Ringsystem mit 5 bis 40 aromatischen Ringatomen, das jeweils durch einen oder mehrere Reste R⁴ substituiert sein kann; dabei können zwei oder mehrere benachbarte Reste R³ miteinander ein mono- oder polycyclisches, aliphatisches, aromatisches oder heteroaromatisches Ringsystem bilden;
R⁴ ist bei jedem Auftreten gleich oder verschieden H, D, F oder ein aliphatischer, aromatischer und/oder heteroaromatischer organischer Rest 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 R⁴ auch miteinander ein mono- oder polycyclisches Ringsystem bilden;
L' ist ein mono- oder bidentater Ligand;
n ist 1 oder 2, wobei n = 1 ist, wenn L' ein bidentater Ligand ist.The invention thus provides a compound according to the following formula (1), Cu (L) (L ') _n formula (1) containing a structure Cu (L) of the following formula (2),

where the symbols and indices used are:
Cu is copper in the oxidation state +1;
X is a neutral nitrogen atom, NR ³ , O or S;
A, when X is a neutral nitrogen atom, is the same or different CR ³ or N at each occurrence, and moreover, exactly one A is CR ³ = CR ³ , NR ³ , O or S; and when X is NR ³ , O or S, each occurrence is the same or different CR ³ or N, with the proviso that at most two A are N;
R ¹ is the same or different at each occurrence H, D, F, Cl, Br, I, N (R ³ ) ₂ , OR ³ , CN, COOR ³ , C (= O) N (R ³ ) ₂ , Si ( R ³ ) ₃ , B (OR ³ ) ₂ , C (= O) R ³ , P (= O) (R ³ ) ₂ , S (= O) R ³ , S (= O) ₂ R ³ , OSO ₂ R ³ , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group each may be substituted with one or more radicals R ³ and wherein one or more non-adjacent CH ₂ groups may be replaced by Si (R ² ) ₂ , C = O, NR ² , O, S or CONR ² , or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more R ³ radicals; while the two radicals R ^{1 can} also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another;
or the two radicals R ¹ , together with the carbon atoms to which they are attached, represent a group of the following formula (3),

where W is the same or different at each occurrence as CR ³ or N, with the proviso that at most two W are N, and the two dashed bonds represent the linkage with the nitrogen atom or the heteroaryl group in the ligand;
R ² is the same or different on each occurrence as a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl Alkenyl or alkynyl group may each be substituted with one or more R ³ groups and wherein one or more non-adjacent CH ₂ groups may be replaced by Si (R ³ ) ₂ , C = O, NR ³ , O, S or CONR ³ may be, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R ³ ;
R ³ is the same or different at each occurrence H, D, F, Cl, Br, I, N (R ⁴ ) ₂ , OR ⁴ , CN, Si (R ⁴ ) ₃ , B (OR ⁴ ) ₂ , C (= O) R ⁴ , P (= O) (R ⁴ ) ₂ , S (= O) R ⁴ , S (= O) ₂ R ⁴ , OSO ₂ R ⁴ , a straight-chain alkyl group having 1 to 20 carbon atoms or a Alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group may be substituted by one or more radicals R ⁴ and wherein one or more non-adjacent CH ₂ groups may be replaced by Si (R ⁴ ) ₂ , C = O, NR ⁴ , O, S or CONR ⁴ , or an aromatic or heteroaromatic ring system having from 5 to 40 aromatic ring atoms, each through one or more Radicals R ⁴ may be substituted; two or more adjacent radicals R ^{3 may} together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system;
R ⁴ is the same or different at each occurrence, H, D, F or an aliphatic, aromatic and / or heteroaromatic organic radical having 1 to 20 carbon atoms, in which also one or more H atoms may be replaced by F; two or more substituents R ^{4 may} also together form a mono- or polycyclic ring system;
L 'is a mono- or bidentate ligand;
n is 1 or 2, where n = 1 when L 'is a bidentate ligand.

In the structure of the formula (2), the drawn circle in the five-membered ring means a 6π electron system as commonly used in organic chemistry.

Although this already follows from the definition of R ² , it should again be emphasized that R ² can not form a ring system with neighboring residues.

According to the invention, the ligand in the structure of the formula (2) coordinates to the copper via an anionic nitrogen atom and the neutral atom X of the heteroaromatic five-membered or six-membered ring, so that the ligand is a monoanionically coordinating ligand.

An aryl group for the purposes of this invention contains 6 to 40 carbon atoms; For the purposes of this invention, 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. Preferably, the heteroaryl group contains 1, 2 or 3 heteroatoms, of which not more than one is selected from O or S. Here, under an aryl group or heteroaryl group either a simpler aromatic Cyclus, ie benzene, or a simple heteroaromatic cycle, for example pyridine, pyrimidine, thiophene, etc., or a fused aryl or heteroaryl group, for example naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc., understood.

An aromatic ring system in the sense of this invention contains 6 to 60 carbon atoms in the ring system. A heteroaromatic ring system in the sense of this invention contains 1 to 60 C atoms and at least one heteroatom in the ring system, with the proviso that the sum of C atoms and heteroatoms gives at least 5. The heteroatoms are preferably selected from N, O and / or S. An aromatic or heteroaromatic ring system in the context of this invention is to be understood as meaning a system which is not necessarily contains only aryl or heteroaryl groups, but in which also several aryl or heteroaryl groups by a non-aromatic unit (preferably less than 10% of the atoms other than H), such as. As a C, N or O atom or a carbonyl group, 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. Furthermore, systems in which two or more aryl or heteroaryl groups are bonded directly to each other, such as. As biphenyl or terphenyl, also be understood as an aromatic or heteroaromatic ring system.

A cyclic alkyl group in the context of this invention is understood as meaning a monocyclic, a bicyclic or a polycyclic group. If several substituents form an aliphatic ring system with one another, the term "aliphatic ring system" for the purposes of the present invention also includes heteroaliphatic ring systems.

In the context of the present invention, a C ₁ - to C ₄₀ -alkyl group in which individual H atoms or CH ₂ groups may be substituted by the abovementioned groups, for example the radicals methyl, ethyl, n-propyl, i Propyl, cyclopropyl, n -butyl, i -butyl, s -butyl, t -butyl, cyclobutyl, 2-methylbutyl, n -pentyl, s -pentyl, t -pentyl, 2-pentyl, neo -pentyl, cyclopentyl, n Hexyl, s -hexyl, t -hexyl, 2-hexyl, 3-hexyl, neo-hexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl , 1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo [2,2,2] octyl, 2-bicyclo [2,2,2] octyl, 2- (2,6-dimethyl) octyl, 3- (3,7-dimethyl) octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1-yl, 1,1-dimethyl-n-hept- 1-yl, 1,1-dimethyl-n-oct-1-yl, 1,1-dimethyl-n-dec-1-yl, 1,1-dimethyl-n-dodec-1-yl, 1,1-dimethyl-n-tetradec-1-yl, 1,1-dimethyl-n-hexadec-1-yl, 1,1-dimethyl-n-octadec-1-yl, 1,1-diethyl - n-hex-1-yl, 1,1-diethyl-n-hept-1-yl, 1,1-diethyl-n-oct-1-yl, 1,1-diethyl-n-dec-1 -yl, 1,1-diethyl-n-dodec-1-yl, 1,1-diethyl-n-tetradec-1-yl, 1,1-diethyln-n-hexadec-1-yl, 1 , 1-diethyl-n-octadec-1-yl, 1- (n-propyl) -cyclohex-1-yl, 1- (n-butyl) -cyclohex-1-yl, 1- (n-hexyl ) -cyclohex-1-yl, 1- (n-octyl) -cyclohex-1-yl and 1- (n-decyl) -cyclohex-1-yl. An alkenyl group is understood as meaning, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl. By an alkynyl group is meant, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl. A C ₁ - to C ₄₀ -alkoxy group is understood as meaning, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, 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 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, benzopyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenofluorene, cis or trans monobenzoindenofluorene, cis or trans dibenzoindenofluorene, truxene, 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, indazole, imidazole, benzimidazole, naphthimidazole, phenanthrimidazole, pyrimididazole, pyrazine imidazole, quinoxaline imidazole, oxazole, benzoxazole , Naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzpyrimidine, 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.

Preferably, the compounds of the invention are characterized in that they are not charged, d. H. electrically neutral. In addition to the ligand L, one or two further ligands L 'are coordinated to the Cu in the compounds according to the invention. Since the compounds according to the invention are Cu (I) complexes and the ligand L is monoanionic, it is therefore preferable if all ligands L 'are neutral.

In this case, the coordination number preferably corresponds overall to the coordination number customary for Cu (I), ie four or, when sterically demanding ligands L 'are used, also three. When L 'is a bidentate ligand, n = 1, resulting in a coordination number of four on the copper. When L 'is a monodentate ligand, n = 1 or 2, where n = 1 may be preferred only for sterically bulky ligands L', but in general n = 2 is preferred.

In the following, preferred embodiments of the structure Cu (L) of the formula (2) are carried out.

wobei A bei jedem Auftreten gleich oder verschieden für CR³ oder N steht und außerdem genau ein A für CR³=CR³, NR³, O oder S steht und die weiteren verwendeten Symbole die oben genannten Bedeutungen aufweisen.In a preferred embodiment of the invention, X is a neutral nitrogen atom. The structure of the formula (2) is therefore preferably a structure of the following formula (4),

wherein A is identical or different for each occurrence for CR ³ or N and also exactly one A is CR ³ = CR ³ , NR ³ , O or S and the other symbols used have the meanings given above.

wobei A in Formel (4a) bis (4c) für NR³, O oder S steht und die weiteren verwendeten Symbole die oben genannten Bedeutungen aufweisen.In this case, at most one symbol A is preferably a heteroatom. Preferred embodiments of the formula (4) are therefore the structures of the formulas (4a) to (4h), the structures of the formulas (4d) to (4h) especially and the structure of the formula (4d) being very particularly preferred,

where A in formula (4a) to (4c) is NR ³ , O or S and the further symbols used have the abovementioned meanings.

wobei die verwendeten Symbole die oben genannten Bedeutungen aufweisen.In a further preferred embodiment, the two groups R ¹ together with the carbon atoms to which they are attached stand for a group of the formula (3). In this case, there is preferably at most one symbol W in the group of the formula (3) for N, and particularly preferably all the symbols W stand for CR ³ . Thus, preference is given to the structures of the following formula (5a) to (5e), the structure of the formula (5a) being particularly preferred,

wherein the symbols used have the meanings given above.

wobei A bei jedem Auftreten gleich oder verschieden für CR³ oder N steht und außerdem genau ein A für CR³=CR³, NR³, O oder S steht und die weiteren verwendeten Symbole die oben genannten Bedeutungen aufweisen.In a preferred embodiment of the formula (5a) to (5e) X is a neutral nitrogen atom. Particularly preferably, it is a structure of the following formula (6)

wherein A is identical or different for each occurrence for CR ³ or N and also exactly one A is CR ³ = CR ³ , NR ³ , O or S and the other symbols used have the meanings given above.

wobei die verwendeten Symbole die oben genannten Bedeutungen aufweisen.Very particular preference is given to the structures of the following formulas (6a) to (6h), the structure of the formula (6d) being particularly preferred,

wherein the symbols used have the meanings given above.

When the groups R ^{1 are} not taken together with the carbon atoms to which they are attached, they represent a group of the formula (3), R ^{1 is} preferably identically or differently selected on each occurrence from the group consisting of H, D, F, one straight-chain alkyl group having 1 to 10 C atoms, preferably having 1 to 5 C atoms, or an alkenyl group having 2 to 10 C atoms, preferably having 2 to 5 C atoms, or a branched or cyclic alkyl group having 3 to 10 C. -Atomen, preferably having 3 to 6 carbon atoms, wherein the alkyl or alkenyl group may be substituted in each case with one or more radicals R ³ , or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably with 6 to 14 aromatic Ring atoms, which may be substituted by one or more radicals R ^{3 in} each case; In this case, the two radicals R ^{1 can} also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another.

In a further preferred embodiment of the invention, the substituent R ^{2 is} selected from the group consisting of a straight-chain alkyl group having 1 to 10 C atoms, preferably having 1 to 5 C atoms, or an alkenyl group having 2 to 10 C atoms, is preferred having 2 to 5 C atoms, or a branched or cyclic alkyl group having 3 to 10 C atoms, preferably having 3 to 6 C atoms, where the alkyl or alkenyl group may each be substituted by one or more radicals R ³ , or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 14 aromatic ring atoms, each of which may be substituted by one or more radicals R ³ . R ² particularly preferably represents an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, in particular an aromatic ring system having 6 to 14 aromatic ring atoms, which may be substituted by one or more radicals R ³ . Examples of suitable aromatic ring systems are selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, fluorene or spirobifluorenyl, which may each be substituted by one or more radicals R ³ .

In a further preferred embodiment of the invention, R ^{3 is} identical or different at each occurrence selected from the group consisting of H, D, F, Cl, Br, CN, a straight-chain alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 C atoms, or an alkenyl group having 2 to 10 C atoms, preferably having 2 to 5 C atoms, or a branched or cyclic alkyl group having 3 to 10 C atoms, preferably having 3 to 6 C atoms, wherein the alkyl or alkenyl group may each be substituted by one or more radicals R ⁴ , but is preferably unsubstituted, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 14 aromatic ring atoms, each by one or more radicals R ⁴ may be substituted, but is preferably unsubstituted; In this case, two or more adjacent radicals R ³ together with a mono- or polycyclic, aliphatic, aromatic or form heteroaromatic ring system. In a particularly preferred embodiment of the invention, R ^{3 is} selected from the group consisting of H, F, Cl, Br, CN, a straight-chain alkyl group having 1 to 5 C atoms or a branched or cyclic alkyl group having 3 to 6 C atoms; in this case, two or more adjacent radicals R ³ together form a mono- or polycyclic aliphatic ring system.

Particularly preferably, the preferences listed above occur simultaneously. Thus, with particular preference for the structures according to the invention of the formulas (2), (4), (4a) to (4h), (5a) to (5e), (6) and (6a) to (6h):
R ¹ , when the groups R ^{1 are} not together with the carbon atoms to which they are attached, represent a group of the formula (3), in each occurrence identically or differently selected from the group consisting of H, D, F, one straight-chain alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl or alkenyl group in each case be substituted by one or more radicals R ³ can, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each of which may be substituted by one or more radicals R ³ ; while the two radicals R ^{1 can} also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another;
R ² is selected from the group consisting of a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, wherein the alkyl or alkenyl group each may be substituted with one or more radicals R ³ , or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may be substituted by one or more radicals R ³ ;
R ³ is the same or different at each occurrence selected from the group consisting of H, D, F, Cl, Br, CN, a straight-chain alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, wherein the alkyl or alkenyl group may each be substituted by one or more radicals R ⁴ , or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, in particular having 6 to 14 aromatic ring atoms which may each be substituted by one or more radicals R ⁴ , but is preferably unsubstituted; in this case, two or more adjacent radicals R ³ together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system.

With very particular preference for the metal complexes according to the invention:
R ¹ , when the groups R ^{1 are} not taken together with the carbon atoms to which they are attached, represent a group of the formula (3), the same or different at each occurrence, selected from the group consisting of H, D, F, one straight-chain alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms or a branched or cyclic alkyl group having 3 to 6 carbon atoms, wherein the alkyl or alkenyl group in each case be substituted by one or more radicals R ³ can, or an aromatic or heteroaromatic ring system having 6 to 14 aromatic ring atoms, each of which may be substituted by one or more radicals R ³ ; In this case, the two radicals R ^{1 can} also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another.
R ² is selected from the group consisting of a straight-chain alkyl group having 1 to 5 C atoms or an alkenyl group having 2 to 5 C atoms or a branched or cyclic alkyl group having 3 to 6 C atoms, wherein the alkyl or alkenyl group each may be substituted with one or more radicals R ³ , or an aromatic or heteroaromatic ring system having 6 to 14 aromatic ring atoms, each of which may be substituted by one or more radicals R ³ ;
R ³ is the same or different at each occurrence selected from the group consisting of H, F, Cl, Br, CN, a straight-chain alkyl group having 1 to 5 carbon atoms or a branched or cyclic alkyl group having 3 to 6 carbon atoms; in this case, two or more adjacent radicals R ³ together form a mono- or polycyclic aliphatic ring system.

In the following, preferred ligands L 'are described. As described above, the ligands L 'are mono- or bidentate ligands, with neutral ligands being preferred, as this produces neutral compounds of formula (1).

Preferred neutral, monodentate ligands L 'are selected from the group consisting of carbon monoxide, nitrogen monoxide, alkyl cyanides, such as. For example, acetonitrile, aryl cyanides, such as. B. benzonitrile, alkyl isocyanides, such as. For example, methylisononitrile, aryl isocyanides, such as. B. benzoisonitrile, amines, such as. For example, trimethylamine, triethylamine, morpholine, phosphines, in particular halogenophosphines, trialkylphosphines, triarylphosphines or alkylarylphosphines, such as. B. trifluorophosphine, trimethylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, triphenylphosphine, tris (pentafluorophenyl) phosphine, dimethylphenylphosphine, methyldiphenylphosphine, bis (tert-butyl) phenylphosphine, phosphites, such as. For example, trimethyl phosphite, triethyl phosphite, arsines, such as. Trifluorarsine, trimethylarsinq, tricyclohexylarsine, tri-tert-butylarsine, triphenylarsine, tris (pentafluorophenyl) arsine, stibines, such as. Trifluorostibine, trimethylstibine, tricyclohexylstibine, tritert-butylstibine, triphenylstibin, tris (pentafluorophenyl) stibine, nitrogen-containing heterocycles, such as. As pyridine, pyridazine, pyrazine, pyrimidine, triazine, and carbenes, in particular Arduengo carbenes.

Preferred neutral, bidentate ligands L 'are selected from diamines, such as. Ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, propylenediamine, N, N, N', N'-tetramethylpropylenediamine, cis- or trans -diaminocyclohexane, cis- or trans-N, N, N ', N '-Tetramethyldiaminocyclohexan, imines, such as. B. 2- [1- (phenylimino) ethyl] pyridine, 2- [1- (2-methylphenylimino) ethyl] pyridine, 2- [1- (2,6-di-iso -propylphenylimino) ethyl] pyridine, 2- [1- (methylimino) ethyl] pyridine, 2- [1- (ethylimino) ethyl] pyridine, 2- [1- (iso -propylimino) ethyl] pyridine, 2- [1- (tert-butylimino) ethyl] pyridine, Diimines, such as. B. 1,2-bis (methylimino) ethane, 1,2-bis (ethylimino) ethane, 1,2-bis (isopropylimino) ethane, 1,2-bis (tert-butylimino) ethane, 2,3-bis ( methylimino) butane, 2,3-bis (ethylimino) butane, 2,3-bis (iso-propylimino) butane, 2,3-bis (tert-butylimino) butane, 1,2-bis (phenylimino) ethane, 1, 2-bis (2-methylphenylimino) ethane, 1,2-bis (2,6-di-iso-propylphenylimino) ethane, 1,2-bis (2,6-di-tert-butylphenylimino) ethane, 2,3- Bis (phenylimino) butane, 2,3-bis (2-methylphenylimino) butane, 2,3-bis (2,6-di-iso-propylphenylimino) butane, 2,3-bis (2,6-di-tert-butyl) butylphenylimino) butane, heterocycles containing two nitrogen atoms, such as. B. 2,2'-bipyridine, o-phenanthroline, or diphosphines, such as. Bis (diphenylphosphino) methane, bis (diphenylphosphino) ethane, bis (diphenylphosphino) propane, bis (diphenylphosphino) butane, bis (dimethylphosphino) methane, bis (dimethylphosphino) ethane, bis (dimethylphosphino) propane, bis (diethylphosphino) methane, Bis (diethylphosphino) ethane, bis (diethylphosphino) propane, bis (di-tert-butylphosphino) methane, bis (di-tert-butylphosphino) ethane or bis (tert-butylphosphino) propane.

Particularly preferred ligands L 'are mono- and diphosphines, especially diphosphines.

The abovementioned preferred embodiments can be combined with one another as desired. In a particularly preferred embodiment of the invention, the abovementioned preferred embodiments apply simultaneously.

Examples of suitable compounds of the formula (1) according to the invention are the structures listed in the table below.

Another object of the present invention is a process for preparing the compounds of the invention by reacting the corresponding free ligand L in protonated or deprotonated form and ligands L 'with suitable copper salts, optionally in the presence of a base. The process can also be carried out in two steps, wherein the ligand L is deprotonated in a first step and is reacted in the second step with a suitable copper salt.

Suitable and preferred copper salts for the preparation of the corresponding copper complexes are Cu mesityl, Cu amides, Cu [N (CH ₂ ) ₄ ] (Cu-pyrrolidine) or [Cu (NC-CH ₃ ) ₄ ] BF ₄ .

By this method, optionally followed by purification, such. As recrystallization or sublimation, the compounds of the invention in high purity, preferably more than 99% (determined by means of ¹ H-NMR and / or HPLC).

For the processing of the compounds according to the invention from the liquid phase, for example by spin coating or by printing processes, formulations of the metal complexes according to the invention are required. These formulations may be, for example, solutions, dispersions or emulsions. It may be preferable to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesitylene, tetralin, hexamethylindane, veratrole, 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.

Yet another object of the present invention is therefore a formulation containing at least one compound of the invention and at least one further compound. The further compound may for example be a solvent. 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 compounds of the invention described above can be used in electronic devices as the active component. Another object of the invention is therefore the use of a compound of the invention in an electronic device. Yet another object of the present invention is an electronic device containing at least one compound of the invention.

An electronic device is understood to mean a device which contains anode, cathode and at least one layer, this layer containing at least one organic or organometallic compound. The electronic device according to the invention thus contains anode, cathode and at least one layer which contains at least one compound according to the invention. 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). 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. It is possible that one or more hole transport layers are p-doped, for example, with metal oxides such as MoO ₃ or WO ₃ or with (per) fluorinated low-electron aromatics, and / or that one or more electron-transport layers are n-doped. 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. Particular preference is given to three-layer systems, the three layers showing blue, green and orange or red emission (for the basic structure see, for example, US Pat. WO 2005/011013 ) or systems which have more than three emitting layers. It may also be a hybrid system wherein one or more layers fluoresce and one or more other layers phosphoresce.

The organic electroluminescent device can be used as a display or for general lighting purposes.

In a preferred embodiment of the invention, the organic electroluminescent device contains the compound according to the invention as an emitting compound in one or more emitting layers.

When the compound of the present invention is used as an emitting compound in an emitting layer, it is preferably used in combination with one or more matrix materials. The mixture of the compound of the invention and the matrix material contains between 0.1 and 99 wt .-%, preferably between 1 and 90 wt .-%, more preferably between 3 and 40 wt .-%, in particular between 5 and 15 wt .-% of Compound of the invention based on the total mixture of emitter and matrix material. Accordingly, the mixture contains between 99.9 and 1 wt .-%, preferably between 99 and 10 wt .-%, particularly preferably between 97 and 60 wt .-%, in particular between 95 and 85 wt .-% of the matrix material based on the total mixture Emitter and matrix material.

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 metal complexes according to the invention are ketones, phosphine oxides, sulfoxides and sulfones, eg. B. according to WO 2004/013080 . WO 2004/093207 . WO 2006/005627 or WO 2010/006680 , Triarylamines, carbazole derivatives, e.g. As CBP (N, N-bis-carbazolylbiphenyl), 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 a plurality of different matrix materials as a mixture, in particular at least one electron-conducting matrix material and at least one hole-conducting matrix material. A preferred combination is, for example, the use of an aromatic ketone, a triazine derivative or a phosphine oxide derivative with a triarylamine derivative or a carbazole derivative as a mixed matrix for the metal complex according to the invention. Also preferred is the use of a mixture of a charge-transporting matrix material and an electrically inert matrix material, which is not or not significantly involved in charge transport, such. In WO 2010/108579 described.

The compounds according to the invention can also be used in other functions in the electronic device, for example as hole transport material in a hole injection or transport layer, as charge generation material, as electron blocking material, as hole blocking material or as electron transport material. Likewise, the compounds according to the invention can be used as matrix material for other phosphorescent metal complexes in an emitting layer.

As 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.). , 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 Mg / Ag, 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.). Likewise suitable for this purpose are organic alkali metal complexes, for. B. Liq (lithium quinolinate). 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 electrodes (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 or partially transparent to allow either the irradiation of the organic material (OSC) or the outcoupling of light (OLED / PLED, O-LASER). Preferred anode materials here are conductive mixed metal oxides. Particularly preferred are indium tin oxide (ITO) or indium zinc oxide (IZO). Also preferred are conductive, doped organic materials, in particular conductive doped polymers, for. B. PEDOT, PANI or derivatives of these polymers. It is furthermore preferred if a p-doped hole transport material is applied to the anode as a hole injection layer, wherein suitable p-dopants are metal oxides, for example MoO ₃ or WO ₃ , or (per) fluorinated electron-poor aromatics. Further suitable p-dopants are HAT-CN (hexacyanohexaazatriphenylene) or the compound NPD9 from Novaled. Such a layer simplifies the hole injection in materials with a low HOMO, ie a HOMO of large magnitude.

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 or even higher, 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. 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 (ink jet printing) can be produced. For this purpose, soluble compounds are necessary, which are obtained for example by suitable substitution. In particular for the polynuclear metal complexes according to the invention, solution processing is preferred because of the high molecular weight.

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. It is thus possible, for example, to apply an emitting layer containing a metal complex according to the invention and a matrix material from solution and then evaporate a hole blocking layer and / or an electron transport layer in vacuo.

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 the metal complexes according to the invention.

• 1. Organische Elektrolumineszenzvorrichtungen enthaltend die erfindungsgemäßen Verbindungen als emittierende Materialien, insbesondere als orange oder rot emittierende Verbindungen, weisen eine hohe Effizienz und Lebensdauer auf. Insbesondere ist so die Herstellung effizienzter OLEDs unter Vermeidung der seltenen Metalle Iridium und Platin möglich.
• 2. Die erfindungsgemäßen Verbindungen sind thermisch stabil und gut sublimierbar. Sie lassen sich daher sowohl durch Sublimation aufreinigen, wie auch bei der Herstellung organischer Elektrolumineszenzvorrichtungen durch Sublimation verarbeiten.
• 3. Die erfindungsgemäßen Verbindungen sind auch gut in organischen Lösemitteln, insbesondere in polaren organischen Lösemitteln, löslich. Dies führt zu einer vereinfachten Aufreinigung während der Synthese der Komplexe. Weiterhin können die erfindungsgemäßen Komplexe dadurch zur Herstellung von OLEDs in lösungsprozessierten Verfahren, beispielsweise Druckverfahren, eingesetzt werden.

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

• 1. Organic electroluminescent devices comprising the compounds of the invention as emitting materials, in particular as orange or red emitting compounds, have a high efficiency and lifetime. In particular, the production of efficient OLEDs while avoiding the rare metals iridium and platinum is possible.
• 2. The compounds according to the invention are thermally stable and readily sublimable. They can therefore be purified both by sublimation, as well as process in the production of organic electroluminescent devices by sublimation.
• 3. The compounds according to the invention are also readily soluble in organic solvents, in particular in polar organic solvents. This leads to a simplified purification during the synthesis of the complexes. Furthermore, the complexes according to the invention can thereby be used for the preparation of OLEDs in solution-processed processes, for example printing processes.

The invention is explained in more detail by the following examples without wishing to restrict them thereby. The person skilled in the art can produce further compounds according to the invention from the descriptions without inventive step, use them in electronic devices and thus carry out the invention in the entire claimed field.

Examples:

The solvents and reagents used can, for. B. from Sigma-ALDRICH or ABCR.

Ligand synthesis

Example 1: Synthesis of the ligand NHA

a) Synthesis of 2-bromo-N-phenylaniline

2-Bromo-N-phenylaniline is prepared by reacting 1-iodo-2-bromo-benzene with aniline using Pd (OAc) ₂ (0.005 equivalent), POP (bis [2- (diphenylphosphino) phenyl] ether) (0.0075 Equivalents) and NaOtBu (1.4 equivalents) in toluene at 130 ° C for 18 h (according to Buden, M., et al., J. Org. Chem. 2009, 74 (12), 4490-4498 ). b) Synthesis of NHA

The synthesis is analogous to D. Knapp et al., J. Am. Chem. Soc. 2009, 131, 6961-6963 , An autoclave is charged with 257.42 mg (1.1 mmol) of 6-methyl-2- (pyridin-2-yl) -1,3,6,2-dioxazaborocane-4,8-dione, 248.12 mg (1 mmol) of 2-bromo- N-phenylaniline, 13.7 mg (0.015 mmol) [Pd ₂ (dba) ₃ ], 16.8 mg (0.06 mmol) PCy ₃ , 90.8 mg (0.5 mmol) Cu (OAc) ₂ and 691.0 mg (5 mmol) K ₂ CO ₃ weighed and rendered inert and 40 ml of DMF and 10 ml of isopropanol was added. The autoclave is closed and the contents are stirred for 24 h at 100.degree. The reaction mixture is taken up in dichloromethane, washed three times with H ₂ O, then the aqueous phase extracted three times with 30 ml dichloromethane, the organic phase dried over MgSO ₄ and concentrated in vacuo. The residue is separated in a silica gel column. Yield 72%.

Example 2: Synthesis of the ligand NBrA

In an autoclave, 514.84 mg (2.2 mmol) of 6-methyl-2- (pyridin-2-yl) -1,3,6,2-dioxazaborocane-4,8-dione, 327.01 mg (1 mmol) of bis (2) bromophenyl) amine, 27.4 mg (0.03 mmol) of [Pd ₂ (dba) ₃ ], 33.6 mg (0.12 mmol) of PCy ₃ , 181.6 mg (1 mmol) of Cu (OAc) ₂ and 1.38 g (10 mmol) of K ₂ CO ₃ weighed and rendered inert and 80 ml of DMF and 20 ml of isopropanol was added. The autoclave is closed and the contents are stirred for 24 h at 100.degree. The reaction mixture is taken up in dichloromethane, washed three times with H ₂ O, then the aqueous phase extracted three times with 30 ml dichloromethane, the organic phase dried over MgSO ₄ and concentrated in vacuo. The residue is separated in a silica gel column. Yield 64%.

complex syntheses

Example 3 Synthesis of [Cu (NHA) (Xantphos)]

To 246.3 mg (1 mmol) of NHA (from Example 1) and 578.6 mg (1 mmol) of Xantphos are added in a glovebox 182.7 mg (1 mmol) of Cu mesityl and 20 ml of toluene. The result is a strong red solution. This is filtered and layered with hexane. It produces dark red crystals. These luminesce intensely red under UV irradiation (356 nm), the solution also luminesces intensely red. Yield: 81%. Elemental analysis calculated (%) for C ₅₆ H ₄₅ CuN ₂ OP ₂ : C, 75.79; H, 5.11; N, 3.16. Found: C, 75.84; H, 4.96; N, 3.02. Example 4 Synthesis of [Cu (NBrA) (Xantphos)]

To 325.2 mg (1 mmol) of NBrA (from Example 2) and 578.6 mg (1 mmol) of Xantphos are added in a glovebox 182.7 mg (1 mmol) of Cu mesityl and 20 ml of toluene. The result is a red solution. This is filtered and layered with hexane. It produces dark red crystals. These luminesce under UV irradiation (356 nm) orange, the solution also luminesces orange. Yield: 78%. ¹ H NMR (DCM-d ₂ , 400.13 MHz): δ 8.22-8.38 (m, 1H), 7.62-7.66 (m, 1H), 7.56-7.60 (m, 1H), 7.40-7.43 (m, 1H), 7.31-7.34 (m, 1H), 6.98-7.27 (m, 27H), 6.83-6.88 (m, 1H), 6.69-6.74 (m, 1H), 6.39-6.48 (m, 1H), 6.32-6.36 (m , 1H), 6.10-6.16 (m, 1H), 5.96-5.99 (m, 1H), 1.88 (s, 3H), 1.58 (s, 3H). ¹³ C { ¹ H} NMR (DCM-d ₂ , 100.13 MHz): δ 161.89, 154.71, 149.39, 138.54, 137.10, 134.37, 134.29, 133.71, 133.15, 132.94, 130.61, 130.51, 130.26, 130.01, 129.54, 129.07, 128.73, 128.65, 128.39, 127.54, 125.80, 125.56, 123.12, 120.03, 119.41, 118.16, 111.62, 36.51, 30.95, 25.32. ³¹ P { ¹ H} NMR (DCM-d ₂ , 161.98 MHz): δ -17.06.

Device Examples

Production of OLEDs (solution-processed devices)

The compounds of the invention can be processed from solution. The production of such components is based on the production of polymeric light-emitting diodes (PLEDs), which has already been described many times in the literature (for example in US Pat WO 2004/037887 ). The structure is composed of substrate / ITO / PEDOT (80 nm) / interlayer (80 nm) / emission layer (60 nm) / ETL (30 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. 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 (EML), the emitters according to the invention are dissolved together with the matrix materials in toluene. The typical solids content of such solutions is between 16 and 25 g / L, if, as here, the typical for a device layer thickness of 60 nm is to be achieved by spin coating. The solution-processed devices contain an emission layer of (polystyrene: M1: M2: emitter) (20%: X%: Y%: 10%). The emission layer is spin-coated in an inert gas atmosphere, in this case argon, and baked at 130 ° C. for 30 minutes. Then an electron transport layer (ETL) (ETM1: ETM2) (50%: 50%) is evaporated in vacuo. Finally, a cathode made of aluminum (100 nm) (high-purity metals from Aldrich, evaporation systems from Lesker, etc., typical vapor pressure 5 × 10 ^-6 mbar) is applied by evaporation. Optionally, first a hole 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 1 summarizes the data obtained. Table 1: Results with solution processed materials Ex. Emitter Ex. X: Y [%] EQE (%) 500 cd / m ² Voltage (V) 500 cd / m ² CIE x / y 500 cd / m ² D-Ex. 1 Example 3 35:35 8.7 5.9 0.60 / 12:38 D-Ex. 2 Example 3 20:50 9.2 5.3 0.61 / 12:37 D-Ex. 3 Example 3 50:20 7.6 6.4 0:59 / 0.39 D-Ex. 4 Example 4 35:35 5.5 6.2 0.57 / 12:41 Table 2: Structural formulas of the materials used

Description of the figures

1 : Single crystal structure of [Cu (NHA) (xantphos)] from Example 3

• a) Lumineszenz im Feststoff: Der Feststoff zeigt rote Emission mit einem Emissionsmaximum bei 609 nm.
• b) Lumineszenz in Lösung in Dichlormethan: Die Lösung zeigt rote Emission mit einem Emissionsmaximum bei 597 nm.
• c) Lumineszenz in einer Polystyrol-Matrix: Die Verbindung in einer Polystyrol-Matrix zeigt rote Emission mit einem Emissionsmaximum bei 594 nm.

2 : Luminescence Properties of [Cu (NHA) (Xantphos)] from Example 3:

• a) Luminescence in the solid: The solid shows red emission with an emission maximum at 609 nm.
• b) Luminescence in solution in dichloromethane: The solution shows red emission with an emission maximum at 597 nm.
• c) Luminescence in a Polystyrene Matrix: The compound in a polystyrene matrix shows red emission with an emission maximum at 594 nm.

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.

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Claims (15)

Compound according to the formula (1), Cu (L) (L ') _n formula (1) containing a structure Cu (L) of the following formula (2),

for the symbols and indices used: Cu is copper in the oxidation state +1; X is a neutral nitrogen atom, NR ³ , O or S; A, when X is a neutral nitrogen atom, is the same or different CR ³ or N at each occurrence, and moreover, exactly one A is CR ³ = CR ³ , NR ³ , O or S; and when X is NR ³ , O or S, each occurrence is the same or different CR ³ or N, with the proviso that at most two A are N; R ¹ is the same or different at each occurrence H, D, F, Cl, Br, I, N (R ³ ) ₂ , OR ³ , CN, COOR ³ , C (= O) N (R ³ ) ₂ , Si ( R ³ ) ₃ , B (OR ³ ) ₂ , C (= O) R ³ , P (= O) (R ³ ) ₂ , S (= O) R ³ , S (= O) ₂ R ³ , OSO ₂ R ³ , a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein the alkyl, alkenyl or alkynyl group each may be substituted with one or more radicals R ³ and wherein one or more non-adjacent CH ₂ groups may be replaced by Si (R ² ) ₂ , C = O, NR ² , O, S or CONR ² , or an aromatic or heteroaromatic ring system with 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R ³ ; while the two radicals R ^{1 can} also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another; or the two radicals R ¹ , together with the carbon atoms to which they are attached, represent a group of the following formula (3),

where W is the same or different at each occurrence as CR ³ or N, with the proviso that at most two W are N, and the two dashed bonds represent the linkage with the nitrogen atom or the heteroaryl group in the ligand; R ² is the same or different on each occurrence as a straight-chain alkyl group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, where the alkyl Alkenyl or alkynyl group may each be substituted with one or more R ³ groups and wherein one or more non-adjacent CH ₂ groups may be replaced by Si (R ³ ) ₂ , C = O, NR ³ , O, S or CONR ³ may be, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, each of which may be substituted by one or more radicals R ³ ; R ³ is the same or different at each occurrence H, D, F, Cl, Br, I, N (R ⁴ ) ₂ , OR ⁴ , CN, Si (R ⁴ ) ₃ , B (OR ⁴ ) ₂ , C (= O) R ⁴ , P (= O) (R ⁴ ) ₂ , S (= O) R ⁴ , S (= O) ₂ R ⁴ , OSO ₂ R ⁴ , a straight-chain alkyl group having 1 to 20 carbon atoms or a Alkenyl or alkynyl group having 2 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl or alkynyl group may be substituted by one or more radicals R ⁴ and wherein one or more non-adjacent CH ₂ groups may be replaced by Si (R ⁴ ) ₂ , C = O, NR ⁴ , O, S or CONR ⁴ , or an aromatic or heteroaromatic ring system having from 5 to 40 aromatic ring atoms, each through one or more Radicals R ⁴ may be substituted; two or more adjacent radicals R ^{3 may} together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system; R ⁴ is the same or different at each occurrence, H, D, F or an aliphatic, aromatic and / or heteroaromatic organic radical having 1 to 20 carbon atoms, in which also one or more H atoms may be replaced by F; two or more substituents R ^{4 may} also together form a mono- or polycyclic ring system; L 'is a mono- or bidentate ligand; n is 1 or 2, where n = 1 when L 'is a bidentate ligand. A compound according to claim 1, characterized in that it is electrically neutral. Compound according to Claim 1 or 2, characterized in that the structure Cu (L) is a structure of the formula (4),

wherein A is identical or different for each occurrence for CR ³ or N and also exactly one A is CR ³ = CR ³ , NR ³ , O or S and the other symbols used have the meanings given in claim 1. Compound according to one or more of Claims 1 to 3, characterized in that the structure Cu (L) is selected from the structures of the formulas (4a) to (4h),

where A in formula (4a) to (4c) is NR ³ , O or S and the other symbols used have the meanings given in claim 1. Compound according to one or more of Claims 1 to 4, characterized in that the structure Cu (L) is chosen from the structures of the formulas (5a) to (5e),

wherein the symbols used have the meanings mentioned in claim 1. Compound according to one or more of Claims 1 to 5, characterized in that the structure Cu (L) is a structure of the formula (6),

wherein A is identical or different for each occurrence for CR ³ or N and also exactly one A is CR ³ = CR ³ , NR ³ , O or S and the other symbols used have the meanings given in claim 1. Compound according to one or more of claims 1 to 6, characterized in that the structure Cu (L) is selected from the structures of the formulas (6a) to (6h),

wherein the symbols used have the meanings mentioned in claim 1. Compound according to one or more of Claims 1 to 7, characterized in that R ¹ is, when the groups R ¹ together with the carbon atoms to which they are attached, represent a group of formula (3), in each case Occurrence identically or differently selected from the group consisting of H, D, F, a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, wherein the alkyl or alkenyl group may each be substituted by one or more radicals R ³ , or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each of which may be substituted by one or more radicals R ³ ; while the two radicals R ^{1 can} also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another; R ² is selected from the group consisting of a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, wherein the alkyl or alkenyl group each may be substituted with one or more radicals R ³ , or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may be substituted by one or more radicals R ³ ; R ³ is the same or different at each occurrence selected from the group consisting of H, D, F, Cl, Br, CN, a straight-chain alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, wherein the alkyl or alkenyl group may each be substituted by one or more R ⁴ , or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, each by one or more radicals R ⁴ may be substituted; in this case, two or more adjacent radicals R ³ together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system. A compound according to one or more of claims 1 to 8, characterized in that L 'is selected from the group consisting of carbon monoxide, nitric oxide, alkyl cyanides, aryl cyanides, alkyl isocyanides, aryl isocyanides, monoamines, monophosphines, arsines, stibines, nitrogen-containing heterocycles, carbenes, diamines , Imines, diimines or diphosphines. A process for preparing a compound according to one or more of claims 1 to 9 by reacting the free ligand L in protonated or deprotonated form and ligands L 'with copper salts, optionally in the presence of a base. Formulation containing at least one compound according to one or more of claims 1 to 9 and at least one further compound and / or a solvent. Use of a compound according to one or more of claims 1 to 9 in an electronic device. Electronic device containing at least one compound according to one or more of claims 1 to 9. An electronic device according to claim 13, 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. Electronic device according to claim 14, which is an organic electroluminescent device, characterized in that the compound according to one or more of claims 1 to 9 is used as an emitting compound in one or more emitting layers.

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