WO2014044347A1 - Metal complexes - Google Patents

Abstract

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

Description

 metal complexes

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

The structure of organic electroluminescent devices (OLEDs), in which organic semiconductors are used as functional materials, is described for example in US 4539507, US 5151629, EP 0676461 and US Pat

WO 98/27136. In the process, organometallic complexes which exhibit phosphorescence instead of fluorescence are increasingly being used as emitting materials (M.A. 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. Generally there are at

There is still room for improvement in OLEDs that show triplet emission, especially in terms of efficiency, operating voltage and lifetime. This applies in particular to yellow-emitting compounds which can be used for two-color white. According to the state of the art, iridium and platinum complexes are used in phosphorescent OLEDs as triplet emitters in particular. Bis- and tris-ortho-metalated complexes with aromatic ligands are used in particular as iridium complexes, the ligands binding to the metal via a negatively charged carbon atom and a neutral nitrogen atom. An example of such a complex is tris- (phenylpyridyl) iridium (III). A variety of related ligands and iridium or platinum complexes are known from the literature. Even if good results have already been achieved with such metal complexes, further improvements are desirable here.

US 2005/0227109 furthermore discloses iridium complexes in which the ligand binds to the metal via a nitrogen atom, for example in a pyridyl group, and the carbon atom of an alkenyl group. Such complexes are also known from Advanced Materials 2004, 16, 2003-2007, with external quantum efficiencies in the range of 4 to 11% are reported. Complexes in which the alkenyl group is part of a cyclic system are not disclosed.

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 have improved properties in terms of efficiency, operating voltage, lifetime, color coordinates and / or color purity, ie. H. Width of the emission band, show. Surprisingly, it has been found that certain metal chelate complexes described in more detail below achieve this object and are suitable for use in an organic electroluminescent device. These metal complexes and organic electroluminescent devices containing these complexes are therefore the subject of the present invention.

The invention thus relates to a compound according to formula (1),

M (L) _n (L ') m formula (1) which contains a partial structure M (L) _n of formula (2), (3) or (4):

Formula (2) Formula (3) Formula (4) where for the symbols and indices used: M is a transition metal; is a heteroaryl group having 5 to 18 aromatic ring atoms, which coordinates to M via a nitrogen atom and which may be substituted by one or more R radicals; is the same or different CR2, C (= O), C (= NR) or BR at each occurrence; is the same or different CR or N at each occurrence; or the two adjacent groups Z in formula (2) or formula (3) stand for a group of the following formula (5),

Y,, Y

 Y-Y

 Formula (5) wherein the dotted bonds indicate the linking of this moiety in the structure of formula (2) and (3), respectively;

Y is the same or different every occurrence CR or N;

R is the same or different at each occurrence H, D, F, Cl, Br, I, N (R ¹ ) ₂ , CN, NO ₂ , OH, COOH, C (= O) N (R ¹ ) ₂ , Si ( R ¹ ) _3> B (OR ¹ ) ₂ , C (= O) R ¹ , P (= O) (R ¹ ) ₂ , S (= O) R ¹ , S (= O) ₂ R, OSO ₂ R ¹ , a straight-chain alkyl, alkoxy or thioaikoxy 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, alkoxy or thioalkoxy group having 3 to 20 C atoms each of which may be substituted with one or more radicals R ¹ , wherein one or more non-adjacent CH ₂ groups are represented by R ¹ C = CR ¹ , C = C, Si (R ¹ ) ₂ , C = O, NR ¹ , O, S or CONR may be replaced and wherein one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each by one or more a plurality of radicals R ¹ may be substituted, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which are replaced by e or more Radicals R ¹ may be substituted, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms which may be substituted by one or more radicals R ¹ , or a diarylamino group, Diheteroarylaminogruppe or Arylheteroarylaminogruppe having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R ¹ ; two or more radicals R may also together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system; is identical or different at each occurrence H, D, F, Cl, Br, I, N (R ² ) ₂ , CN, NO ₂ , 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 having 1 to 20 C. Atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, each of which may be substituted by one or more radicals R ² , wherein a or a plurality of non-adjacent CH ₂ groups can be replaced by R ² C =CR ² , C 1 -C ⁴ , Si (R ² ) ₂ , C =O, NR ² , O, S or CONR ² , and one or more H groups Atoms may be replaced by D, 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 a

Aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R ² , or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R ² , or a Diarylamino, Diheteroarylaminogruppe or Arylheteroarylaminogruppe having 10 to 40 aromatic ring atoms, which may be substituted by one or more radicals R ² ; in this case, two or more adjacent radicals R ¹ with one another or R with R form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic 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 poly---cyclic, aliphatic ring system;

L 'is the same or different any occurrence

 co-ligand; n is 1, 2 or 3; m is 0, 1, 2, 3 or 4; in this case also several ligands L can be linked to one another or L to L 'via a single bond or a divalent or trivalent bridge and thus span a tridentate, tetradentates, pentadentates or hexadentate ligand system; Furthermore, a substituent R can additionally coordinate to the metal.

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. 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.

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 context 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 is 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 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.

For the purposes of this invention, a cyclic alkyl, alkoxy or thioalkoxy group is understood as meaning a monocyclic, a bicyclic or a polycyclic group.

In the context of the present invention, under a C ₁ - to C ₄₀ -alkyl group in which also individual H atoms or CH ₂ groups can be substituted by the abovementioned groups, for example the radicals methyl, ethyl, n-propyl, Propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neo-pentyl, cyclopentyl, n- Hexyl, s -hexyl, t-hexyl, 2-hexyl, 3-hexyl, neo-hexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-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-hexadecyl-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-yl-understood. 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. Under a C to C ₄ o-alkoxy group, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy or 2-methylbutoxy understood.

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, benzpyrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans- indenofluorene, cis- or trans-monobenzoindenofluorene, cis- or trans-dibenzoindenofluorene, Truxen, isotruxene, spirotruxene, spiro-isotruxene, 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, quinoxalinimidazole, 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 diazole, 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.

If the compounds according to the invention are charged, they additionally contain a corresponding counterion, ie one or more anions in the case of a cationic compound of the formula (1) or one or more cations in the case of an anionic compound of the formula (1). Preferably, compounds according to formula (1) are not charged, d. H. electrically neutral, are. This is achieved in a simple way by selecting the charge of the ligands L and L 'in such a way that they compensate for the charge of the complexed metal atom M.

Preference is furthermore given to compounds of the formula (1), characterized in that the sum of the valence electrons around the metal atom in four-coordinate complexes is 16 and in five-coordinated complexes is 16 or 18 and in six-coordinate complexes is 18. This preference is due to the particular stability of these metal complexes.

Preference is given to compounds of the formula (1) in which M is a transition metal, with lanthanides and actinides being excluded, in particular being a tetracoordinate, a pentacoordinate or a hexacoordinate transition metal, more preferably selected from the group consisting of chromium, Molybdenum, tungsten, rhenium,

Ruthenium, osmium, rhodium, iridium, nickel, palladium, platinum, copper, silver and gold, especially molybdenum, tungsten, rhenium, ruthenium, osmium, iridium, copper, platinum and gold. Most preferred are iridium and platinum. The metals can be present in different oxidation states. Preference is given to the abovementioned metals in the oxidation states Cr (0), Cr (II), Cr (III), Cr (IV), Cr (VI), Mo (0), Mo (II), Mo (III), Mo (IV), Mo (VI), W (0), W (II), W (III), W (IV), W (VI), Re (I), Re (II), Re (III), Re (IV), Ru (II), Ru (III), Os (II), Os (III), Os (IV), Rh (I), Rh (III), Ir (I), Ir (III), Ir (IV), Ni (0), Ni (II), Ni (IV), Pd (II), Pt (II), Pt (IV), Cu (I), Cu (II), Cu (III), Ag (I), Ag (II), Au (I), Au (III) and Au (V). Particularly preferred are Mo (0), W (0), Re (I), Ru (Ii), Os (II), Rh (Ili), Cu (I), Ir (III) and Pt (II). Very particular preference is given to Ir (III) and Pt (II).

In the complexes of the formula (1), the indices n and m are chosen such that the coordination number on the metal M in total, depending on the metal, corresponds to the usual coordination number for this metal.

In a preferred embodiment of the invention, M is a tetracoordinate metal, and the subscript n is 1 or 2. When the index n = 1, there are still one bidentate or two monodentate ligands L ', preferably a bidentate ligand L' to which Coordinated metal M. When the index n = 2, the index m = 0. A preferred tetracoordinate metal is Pt (II).

In a further preferred embodiment of the invention, M is a hexacoordinated metal, and the subscript n is 1, 2 or 3, preferably 2 or 3. If the index n = 1, there are still four monodentate or two bidentate or one bidentate and two monodentates or a tridentate and a monodentate or a tetradentate ligand L ', preferably two bidentate ligands L 1 coordinated to the metal. When the index n = 2, one more bidentate or two monodentate ligand L ', preferably a bidentate ligand L', is coordinated to the metal. When the index n = 3, the index m = 0. A preferred hexacoordinated metal is Ir (III).

In a preferred embodiment of the invention, the substructure M (L) _{n is} selected from the structures of the formulas (2) and (3), in particular of the formula (2).

In a further preferred embodiment of the invention, the two groups Z in formula (2) or in formula (3) represent a group of the abovementioned formula (5). The substructure M (L) _n is therefore preferably a structure of the following formula (6) or (7),

 Formula (6) Formula (7) wherein the symbols and indices used are those mentioned above

 Have meanings.

In a preferred embodiment of the invention in formula (5) or (6) or (7) a maximum of two groups Y for N, the other groups Y stand for CR. More preferably, at most one group Y is N, and very particularly preferably all groups Y are CR, according to the structures of the formula (6a) or (7a),

 Formula (6a) Formula (7a) where the symbols and indices used are those mentioned above

 Have meanings.

In a further preferred embodiment of the invention, A in formula (2) to (4) or (6), (6a), (7) and (7a) is CR ₂ . Thus structures of the following formulas (6b) and (7b) are preferred,

 Formula (6b) Formula (7b) where the symbols and indices used are those mentioned above

Have meanings.

When A is CR 2, R in this group, identically or differently on each occurrence, preferably stands for a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, each with one or more radicals R may be substituted with one or more non-adjacent CH ₂ groups by R ¹ C = CR ¹ , C ^ C, Si (R ¹ ) ₂ , C = 0, NR ¹ , O, S or CONR ¹ may be replaced and wherein one or more H atoms may be replaced by D, F, Cl, Br, I or CN, 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 aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R ¹ ; In this case, the radicals R can also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another.

If the radicals R together form a ring system, this creates a spiro system. Examples of preferred spiro systems are shown in the following formulas (8), (9) and (10) for the basic structure of the formula (2), whereby such spiro systems are accessible quite analogously also with structures of the formula (3) or (4) :

 Formula (8) Formula (9) Formula (10) wherein the symbols and indices used are those mentioned above

Have meanings, p = 0, 1, 2, 3 or 4 and the CH ₂ groups in formula (8) or the phenyl groups in formula (9) and (10) may also be substituted by one or more radicals R ¹ ,

When A is BR, R preferably represents 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 . In this case, the aryl group which binds directly to the boron atom is preferably substituted in at least one ortho position, preferably at both ortho positions, to the boron atom, in particular by an alkyl group having 1 to 10 C atoms. Suitable groups here are, for example, ortho-tolyl, 2,6-xylyl or 2,4,6-mesityl.

In a further preferred embodiment of the invention, CyN is a heteroaryl group having 5 to 13 aromatic ring atoms, particularly preferably having 5 to 10 aromatic ring atoms, which coordinates to M via a neutral nitrogen atom and which may be substituted by one or more radicals R.

Preferred embodiments of the group CyN are the structures of the following formulas (CyN-1) to (CyN-7), wherein the group CyN in each case binds to the cyclopentadiene or indene of the ligand at the position indicated by # and to the position indicated by ^* coordinated to the metal,

 (CyD-5) (CyD-6) (CyD-7) where R has the abovementioned meanings and furthermore:

X is the same or different CR or N at each occurrence;

W is the same or different NR, O or S at each occurrence.

Preferably, a maximum of three symbols X in CyN stands for N, more preferably at most two symbols X in CyN stand for N, very particularly preferably at most one symbol X in CyN stands for N. More preferably, all symbols X stand for CR.

Particularly preferred groups CyN are thus the groups of the following formulas (CyN-1a) to (CyN-7a),

wherein the symbols used have the meanings given above.

Preferred groups among the groups (CyN-1) to (CyN-10) are the groups (CyN-1), (CyN-3) and (CyN-4), and particularly preferred are the groups (CyN-1 a), (CyN-3a) and (CyN-4a).

If radicals R are bonded in the substructure of the formula (2) to (4), then these radicals R at each occurrence are the same or different preferably selected from the group consisting of H, D, F, Br, I, N (R ¹ ) ₂ , CN, Si (R ¹ ) ₃ , B (OR ¹ ) _2> C (= O) R ¹ , a straight chain alkyl group of 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, each of which may be substituted by one or more radicals R ¹ , wherein one or more H atoms by D or F can be replaced, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R ¹ each; two adjacent radicals R or R with R ^{1 can} also form a mono- or polycyclic, aliphatic or aromatic ring system with one another. With particular preference, these radicals R on each occurrence are identically or differently selected from the group consisting of H, D, F, N (R ¹ ) ₂ , a straight-chain alkyl group having 1 to 6 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms, wherein one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which may be substituted by one or more radicals R ¹ ; in this case, two adjacent radicals R or R with R ^{1 can} also form a mono- or polycyclic, aliphatic or aromatic ring system with one another. In a preferred embodiment of the invention, two adjacent radicals R together form an aliphatic cycle containing no acidic benzylic protons, in particular an aliphatic five-membered ring without acidic benzylic protons. The absence of acidic benzylic protons can be achieved by substitution of the benzylic positions or by the use of corresponding bicycles, in which due to the fixed geometry the benzylic protons are not acidic.

It is also possible that two or more Rs bound to CyN and to A and Z, respectively, form a ring with each other.

This is exemplified by structures of the following formulas (1 1) to (17) for structures of formula (2),

where the symbols and indices used have the abovementioned meanings and Q is the same or different CR ¹ or N at each occurrence. CyN has the same meaning as listed above, although it specifically indicates two carbon atoms and one nitrogen atom. In this case, the above-mentioned structures, for example, the benzo rings in the bridging units, by one or more radicals R ¹ may be substituted. For structures of the formula (3), the ring formation of the radicals is shown by way of example by the structures of the following formulas (18) and (19),

 Formula (18) Formula (19) wherein the symbols and indices used are those mentioned above

Have meanings.

For structures of the formula (4), the ring formation can be carried out analogously to structures of the formula (3).

Furthermore, it is possible that the substituent R, which is adjacent to the position for metal coordination, represents a group which also coordinates to the metal M or binds. Preferred coordinating groups R are aryl or heteroaryl groups, for example phenyl or pyridyl, aryl or alkyl cyanides, aryl or alkyl isocyanides, amines or amides, alcohols or alcoholates, thioalcohols or thioalcoholates, phosphines, phosphites, carbonyl functions, carboxylates, carbamides or Aryl or alkyl acetylides.

As described above, instead of one of the radicals R, a bridging unit may be present which links this ligand L with one or more further ligands L and L '. In a preferred embodiment of the invention, instead of one of the radicals R, in particular instead of the radicals R, in the ortho or meta position to the coordinating

Atom, a bridging unit exists, so that the ligands have tridentate or polydentate or polypodalen character. There may also be two such bridging units. This leads to the formation of macrocyclic ligands or to the formation of cryptates. Preferred structures with polydentate ligands or with polydentate ligands are the metal complexes of the following formulas (20) to (27),

 Formula (24) Formula (25)

Formula (26) ^Formula ( ²⁷ ) wherein the symbols and indices used are those mentioned above

Have meanings. The above-mentioned formulas (20) to (27) relate only to complexes having a partial structure of the formula (2). Analogously, tri- and tetradentate ligands or polypodal ligands having partial structures of the formula (3) or (4) are accessible. For ligands having partial structures of the formula (3), the linkage via the group A is furthermore possible, as shown schematically in the following compound of the formula (28):

 Formula (28) wherein the symbols and indices used are those mentioned above

Have meanings.

In this case, in the structures of the formulas (20) to (28), V preferably represents a single bond or a bridging unit containing 1 to 80 atoms from the third, fourth, fifth and / or sixth main group (group 13, 14, 15 or 16 according to IUPAC) or a 3- to 6-membered homo- or heterocycle which covalently connects the partial ligands L with each other or L with L '. In this case, the bridging unit V can also be constructed asymmetrically, ie the combination of V to L or L 'does not have to be identical. The bridging unit V may be neutral, single, double or triple negative or single, double or triple positively charged. V is preferably neutral or simply negative or simply positively charged, more preferably neutral. The charge of V is preferably chosen so that a total of a neutral complex is formed. In this case, the preferences mentioned above for the substructure ML _n apply to the ligands and n is preferably at least 2.

The exact structure and chemical composition of group V has no significant influence on the electronic properties of the complex, as the task of this group is essentially to: by bridging L with each other or with L 'to increase the chemical and thermal stability of the complexes.

If V is a trivalent group, ie three ligands L are bridged with one another or two ligands L with L 'or one ligand L with two ligands L', V is preferably the same or different at each occurrence selected from the group consisting of B, B ( R ¹ ) ^~ B (C (R ¹ ) ₂ ) 3,

(R ¹ ) B (C (R ¹ ) ₂ ) ₃ -, B (O) ₃ , (R ¹ ) B (O) ₃ -, B (C (R) ₂ C (R ¹ ) ₂ ) ₃ , ( R ¹ ) B (C (R ¹ ) ₂ C (R ¹ ) ₂ ) ₃ -, B (C (R ¹ ) ₂ O) ₃ , (R) B (C (R ¹ ) ₂ O) ₃ -, B (OC (R) ₂ ) ₃ , (R) B (OC (R ¹ ) ₂ ) ₃ -, C (R ¹ ), CO ^" CN (R ¹ ) ₂ , (R ¹ ) C (C (R) ₂ ) ₃ , (R ¹ ) C (O) ₃ , (R ¹ ) C (C (R) ₂ C (R ¹ ) ₂ ) ₃ ¹ (R) C (C (R ¹ ) ₂ O) ₃ , (R ¹ ) C (OC (R ¹ ) ₂ ) ₃ , (R ¹ ) C (Si (R ¹ ) ₂ ) ₃ , (R) C (Si (R ¹ ) ₂ C (R ¹ ) ₂ ) ₃ ,

(R ¹ ) C (C (R ¹ ) ₂ Si (R ¹ ) ₂ ) ₃ , (R ¹ ) C (Si (R) ₂ Si (R ¹ ) ₂ ) ₃ , Si (R ¹ ), (R ¹ ) Si (C (R) ₂ ) ₃ , (R ¹ ) Si (O) ₃ , (R) Si (C (R ¹ ) ₂ C (R ¹ ) ₂ ) ₃ , (R ¹ ) Si (OC (R ¹ ) ₂ ) ₃ , (R ¹ ) Si (C (R ¹ ) ₂ O) ₃ , (R ¹ ) Si (Si (R ¹ ) ₂ ) ₃ , (R ¹ ) Si (Si (R ¹ ) ₂ C (R ¹ ) ₂ ) ₃ , (R ¹ ) Si (C (R ¹ ) ₂ Si (R ¹ ) ₂ ) ₃ ,

(R ¹ ) Si (Si (R ¹ ) ₂ Si (R ¹ ) ₂ ) ₃ , N, NO, N (R) \ N (C (R ¹ ) ₂ ) ₃ , (R ¹ ) N (C (R ¹ ) ₂ ) ₃ ⁺ ,

N (C = O) ₃ , N (C (R ¹ ) ₂ C (R ¹ ) ₂ ) ₃ , (R ¹ ) N (C (R ¹ ) ₂ C (R ¹ ) ₂ ) ⁺ , P, P ( R ¹ ) ⁺ , PO, PS,

P (O) ₃ , PO (O) ₃ , P (OC (R ¹ ) ₂ ) ₃ , PO (OC (R ¹ ) ₂ ) ₃ , P (C (R ¹ ) ₂ ) ₃ , P (R) ( C (R ¹ ) ₂ ) ₃ ⁺ , PO (C (R) ₂ ) ₃₎ P (C (R) ₂ C (R) ₂ ) ₃ , P (R ¹ ) (C (R ¹ ) ₂ C (R ) ₂ ) ₃ ⁺ , PO (C (R ¹ ) ₂ C (R ¹ ) ₂ ) ₃ , S ⁺ , S (C (R ¹ ) ₂ ) ₃ ⁺ , S (C (R ¹ ) ₂ C (R ¹ ₂ ) ₃ ⁺ ,

or a unit according to formula (29) to (33),

 Formula (29) Formula (30) Formula (31)

Formula (32) Formula (33) wherein the dashed bonds each indicate the bond to the partial ligands L and L 'and Z is the same or different at each occurrence selected from the group consisting of a single bond, O, S, S (= 0), S (= 0) _2> NR ¹ , PR ¹ , P (= 0) R ¹ , C (R ¹ ) ₂ , C (= 0), C (= NR ¹ ), C (= C (R ¹ ) ₂ ), Si (R ¹ ) ₂ or BR ¹ . The other symbols used have the meanings given above.

If V stands for a group CR ₂ , the two radicals R can also be linked to one another so that structures such as, for example, 9,9-fluorene are suitable groups V.

If V is a divalent group, ie two ligands L linked to one another or a ligand L to L ', V is preferably identical or different in each occurrence selected from the group consisting of BR ¹ , B (R ¹ ) ₂ ^- , C ( R ¹ ) ₂ , C (= 0), Si (R ¹ ) ₂ , NR ¹ , PR ¹ , P (R ¹ ) ₂ ⁺ , P (= O) (R ¹ ), P (= S) (R ¹ ), O, S, Se, or a unit of formula (34) to (43),

Formula (42) wherein the dashed bonds in each case indicate the bond to the partial ligands L and L ', Y is identical or different on each occurrence for C (R ¹ ) ₂ , N (R ¹ ), O or S. and the other symbols used in each case have the meanings given above. In the following, preferred ligands L 'are described as they occur in formula (1). Correspondingly, the ligand groups L 'can also be selected if these are bonded to L via a bridging unit V, as indicated in formulas (22), (24), (26) and (28). The ligands L 'are preferably neutral, monoanionic, dianionic or trianionic ligands, particularly preferably neutral or monoanionic ligands. They may be monodentate, bidentate, tridentate or tetradentate and are preferably bidentate, so preferably have two coordination sites. As described above, the ligands L 'may also be bonded to L via a bridging group V.

Preferred neutral, monodentate ligands U 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. 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, trimethylarsine, tricyclohexylarsine, tri-tert-butylarsine, triphenylarsine, tris (pentafluorophenyl) -arsine, stibines, such as. Trifluorostibine, trimethylstibine, tricyclohexylstibine, tri-ferf-butylstibine, triphenylstibin, tris (pentafluorophenyl) stibine, nitrogen-containing heterocycles, such as. As pyridine, pyridazine, pyrazine, pyrimidine, triazine, and carbenes, in particular Arduengo carbenes.

Preferred monoanionic, monodentate ligands L 'are selected from hydride, deuteride, the halides F, Cl, ^"ΒΓ and Γ, Alkylacetyliden such. B. Methyl C = C ^{~, tert-butyl-CsC"} Arylacetyliden as z. As phenyl C = C ^~ , cyanide, cyanate, isocyanate, thiocyanate, isothiocyanate, aliphatic or aromatic alcoholates, such as. For example, methanolate, ethanolate,

Propanolate, / so-propanolate, fert-butylate, phenolate, aliphatic or aromatic thioalcoholates such. Methanethiolate, ethanethiolate, Propanethiolate, / so-propanethiolate, ferf-thiobutylate, thiophenolate, amides, such as. Dimethylamide, diethylamide, di-propylamide, morpholide,

Carboxylates, such as. Acetate, trifluoroacetate, propionate, benzoate,

Aryl groups, such as. Phenyl, naphthyl, and anionic nitrogen-containing heterocycles such as pyrrolidine, imidazolide, pyrazolide. The alkyl groups in these groups are preferably C 1 -C 20 -alkyl groups, particularly preferably C 1 -C 10 -alkyl groups, very particularly preferably C 1 -C ₄ -alkyl groups. An aryl group is also understood to mean heteroaryl groups. These groups are as defined above. Preferred di- or trianionic ligands are O ^2- , S ^{2 ~} carbides, which lead to a coordination of the form RC ^ M, and nitrenes, which lead to a coordination of the form RN = M, where R is generally a substituent, or N ^{3. "Preferred} neutral or mono- or dianionic, bidentate or higher-dentate ligand L 'are selected from diamines, such as. for example, ethylene diamine, Ν, Ν, ^Ν', Ν ^{'tetramethylethylenediamine,} propylenediamine, Ν , Ν, Ν ^' , Ν ^' - tetramethylpropylenediamine, cis- or trans -diaminocyclohexane, cis- or trans-N, N, N ', N'-tetramethyldiaminocyclohexane, imines, such as, for example, 2- [1- (phenylimino) ethyl] pyridine, 2- [1- (2-methylphenylimino) ethyl] pyridine, 2- [1- (2,6-di-propylphenylimino) ethyl] pyridine, 2- [1- (methylimino) ethyl] pyridine, 2- [1- (ethylimino) ethyl] pyridine, 2- [1- (/ so-propylimino) ethyl] pyridine, 2- [1- (tert-butylimino) ethyl] pyridine, diimines, such as 1, 2-bis (methylimino) ethane, 1, 2-bis (ethylimino) ethane, 1, 2-bis (/ so-propylimino) ethane, 1, 2-bis (fer f-butyl-imino) ethane, 2,3-bis (methylimino) butane, 2,3-bis (ethylimino) butane, 2,3-bis (/ so-propylimino) butane, 2,3-bis (ethylenediamine) butylimino) butane, 1, 2-bis (phenylimino) ethane,, 2-bis (2-methylphenylimino) ethane,, 2-bis (2,6-di- / so-propylphenyl-imino) ethane, 1, 2 Bis (2,6-di-ferf-butylphenylimino) ethane, 2,3-bis (phenyl-imino) butane, 2,3-bis (2-methylphenylimino) butane, 2,3-bis (2,6-bis) / ^' so-propyl-phenylimino) butane, 2,3-bis (2,6-di-feri-butylphenylimino) butane, heterocycles containing two nitrogen atoms, such as. As ^{2,2-bipyridine,}

o-phenanthroline, 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 (terf-butylphosphino) methane, bis (di-tert-butylphosphino) ethane, bis (fer-butylphosphino) propane, 1,3-diketonates derived from 1 , 3-diketones, such. As acetylacetone, benzoylacetone, 1, 5-diphenylacetylacetone, dibenzoyl methane, bis (1,1-trifluoroacetyl) methane, 3-ketonates derived from

3-keto esters, such. For example, ethyl acetoacetate, carboxylates derived from aminocarboxylic acids, such as. As pyridine-2-carboxylic acid, quinoline-2-carboxylic acid, glycine, Ν, Ν-dimethylglycine, alanine, N, N-dimethylamino-alanine, salicyliminates derived from salicylimines, such as. As methylsalicylimine, ethylsalicylimine, phenylsalicylimine, dialcoholates derived from dialcohols, such as. For example, ethylene glycol, 1, 3-propylene glycol, dithiolates derived from dithiols, such as. 1, 2-ethylenedithiol, 1, 3-propylenedithiol, bis (pyrazolylborates), bis (imidazolyl) borates, 3- (2-pyridyl) -diazoles or 3- (2-pyridyl) -triazoles. Preferred tridentate ligands are borates of nitrogen-containing heterocycles, such as. As tetrakis (1-imidazolyl) borate and tetrakis (1-pyrazolyl) borate.

Also preferred are bidentate monoanionic, neutral or dianionic ligands L ', in particular monoanionic ligands which have with the metal a cyclometallated five-membered ring or six-membered ring with at least one metal-carbon bond, in particular a cyclometallated five-membered ring. These are in particular ligands as are generally used in the field of phosphorescent metal complexes for organic electroluminescent devices, ie ligands of the type phenylpyridine, naphthylpyridine, phenylquinoline, phenylisoquinoline, etc., which may each be substituted by one or more radicals R. The person skilled in the field of phosphorescent

Electroluminescent devices, a plurality of such ligands is known, and he can without further inventive step other such

Select ligands as ligand L 'for compounds according to formula (1). In general, it is particularly suitable for the combination of two groups, as shown by the following formulas (44) to (68), wherein one group preferably binds via a neutral nitrogen atom or a carbene carbon atom and the other group preferably via a negatively charged Carbon atom or a negatively charged nitrogen atom binds. The ligand L 'can then be formed from the groups of formulas (44) to (68) by each of these groups bonding to each other at the position indicated by #. The position at which the groups coordinate to the Metali are indicated by ^* . These groups can also be bound to the ligand L via one or two bridging units V.

F

ormel (44) Formula (45) Formula (47) Formula (48)

Formula (49) Formula (50) Formula (51) Formula (52) Formula (53)

 Formula (54) Formula (55) Formula (56) Formula (57)

Formula (58)

Formula (59) Formula (60) Formula (61) Formula (62) Formula (63)

Formula (64) Formula (65) Formula (66) Formula (67) Formula (68) Where W, X and R have the same meaning as described above. 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.

Also preferred ligands U are r | ⁵ cyclopentadienyl, r | ^5- pentamethylcyclopentadienyl, η ⁶ -ββηζοΙ or Ti ⁷ -cycloheptatrienyl, which may each be substituted by one or more radicals R.

Also preferred ligands L 'are 1,3,5-cis, cis-cyclohexane derivatives, in particular of the formula (69), 1,1,1-tri (methylene) methane derivatives, in particular of the formula (70) and 1, 1, 1- trisubstituted methanes, in particular of the formulas (71) and (72),

where in each case the coordination to the metal M is shown in the formulas, R has the abovementioned meaning and A, identical or different at each occurrence, is Cr, S ^" , COO, PR ₂ or NR ₂ .

Preferred radicals R in the structures listed above are identically or differently selected on each occurrence from the group consisting of H, D, F, Br, N (R ¹ ) ₂ , CN, B (OR ¹ ) ₂ , C (= 0) R ¹ , P (= O) (R ¹ ) ₂ , a straight-chain alkyl group having 1 to 10 C atoms or an alkenyl or alkynyl group having 2 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms which may each be substituted by one or more radicals R ¹ , wherein one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 14 aromatic ring atoms, each represented by one or more radicals R ¹ may be substituted; two or more adjacent radicals R can also be included form a mono- or polycyclic, aliphatic, aromatic and / or benzoannelliertes ring system. Particularly preferred radicals R are the same or different at each occurrence selected from the group consisting of H, D, F, Br, CN, B (OR ¹ ) ₂ , a straight-chain alkyl group having 1 to 5 carbon atoms, in particular methyl, or a branched or cyclic alkyl group having 3 to 5 C-atoms, in particular iso-propyl or tert-butyl, wherein one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 12 aromatic ring atoms, the each may be substituted by one or more radicals R; two or more radicals R may also together form a mono- or polycyclic, aliphatic, aromatic and / or benzoannulated ring system.

The complexes according to the invention can be facial or pseudofacial, or they can be meridional or pseudomeridional.

The ligands L may also be chiral depending on the structure. This is particularly the case when they contain substituents, for example alkyl, alkoxy, dialkylamino or aralkyl groups, which have one or more stereocenters. Since the basic structure of the complex can also be a chiral structure, the formation of diastereomers and several pairs of enantiomers is possible. The complexes according to the invention then comprise both the mixtures of the different diastereomers or the corresponding racemates as well as the individual isolated diastereomers or enantiomers.

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 according to the invention are the compounds listed in the following table.

The metal complexes according to the invention can in principle be prepared by various methods. However, the methods described below have been found to be particularly suitable.

Therefore, another object of the present invention is a process for the preparation of the metal complex compounds according to formula (1) by reacting the corresponding free ligands L and optionally L 'with metal alcoholates of the formula (73), with metal ketoketonates of the formula (74), with metal halides of the formula (75), with dimeric metal complexes of the formula (76) or with metal complexes of the formula (77),

 Formula (73) Formula (74) Formula (75)

 (Anion)

Formula (76) F ° ^{sleeves (77)} where the symbols M, m, n and R have the meanings indicated above, Hal = F, Cl, Br or I, L 'is an alcohol, especially an alcohol having 1 to 4 C atoms or a nitrile, in particular acetonitrile or benzonitrile, and (anion) is a non-coordinating anion, such as triflate.

It is also possible to use metal compounds, in particular iridium compounds, which carry both alcoholate and / or halide and / or hydroxyl and also ketoketonate radicals. These connections can also be loaded. Corresponding iridium compounds which are particularly suitable as starting materials are disclosed in WO 2004/085449.

Especially suitable are [IrCl ₂ (acac) 2r, for example Na [IrCl ₂ (acac) ₂ ], metal complexes with acetylacetonate derivatives as ligands, for example Ir (acac) 3 or tris (2,2,6,6-tetramethylheptane-3 , 5-dionato) iridium, and lrCl ₃ xH ₂ O, where x is usually a number between 2 and 4.

Suitable platinum starting materials are, for example, PtCl ₂ , K ₂ [PtCl ₄ ],

PtCl ₂ (DMSO) ₂ , Pt (Me) ₂ (DMSO) ₂ or PtCl ₂ (benzonitrile) ₂ . The synthesis of the complexes is preferably carried out as in WO

2002/060910, WO 2004/085449 and WO 2007/065523.

Heteroleptic complexes can also be used, for example, according to WO

2005/042548 be synthesized. The synthesis can be activated, for example, thermally, photochemically, in an autoclave and / or by microwave radiation. In a preferred embodiment In the invention, the reaction is carried out without the use of an additional solvent in the melt. Here, "melt" means that the ligand has melted and the metal precursor is dissolved or suspended in this melt

Furthermore, it is also possible to add a Lewis acid, for example a silver salt or AICI ₃ .

By these methods, optionally followed by purification, such. As recrystallization or sublimation, the compounds of the invention according to formula (1) can be obtained in high purity, preferably more than 99% (determined by means of ¹ H-NMR and / or HPLC).

The compounds according to the invention can also be made soluble by suitable substitution, for example by longer alkyl groups (about 4 to 20 C atoms), in particular branched alkyl groups, or optionally substituted aryl groups, for example xylyl, mesityl or branched terphenyl or quaterphenyl groups. Such compounds are then soluble in common organic solvents, such as toluene or xylene at room temperature in sufficient concentration to process the complexes from solution can. These soluble compounds are particularly suitable for processing from solution, for example by printing processes.

The compounds of the invention may also be mixed with a polymer. It is also possible to incorporate these compounds covalently into a polymer. This is particularly possible with compounds which are substituted with reactive leaving groups, such as bromine, iodine, chlorine, boronic acid or boronic acid esters, or with reactive, polymerizable groups, such as olefins or oxetanes. These can be used as monomers for the production of corresponding oligomers, dendrimers or polymers. The oligomerization or polymerization is preferably carried out via the halogen functionality or the boronic acid functionality or via the polymerizable group. It is also possible to crosslink the polymers via such groups. The compounds of the invention and polymers can be used as a crosslinked or uncrosslinked layer. The invention therefore further oligomers, polymers or dendrimers containing one or more of the compounds of the invention listed above, wherein one or more bonds of the inventive compound to the polymer, oligomer or dendrimer are present. Depending on the linkage of the compound according to the invention, this therefore forms a side chain of the oligomer or polymer or is linked in the main chain. The polymers, oligomers or dendrimers may be conjugated, partially conjugated or non-conjugated. The oligomers or polymers may be linear, branched or dendritic. The repeat units of the compounds according to the invention in oligomers, dendrimers and polymers have the same preferences as described above.

To prepare the oligomers or polymers, the monomers according to the invention are homopolymerized or copolymerized with further monomers. Preference is given to copolymers in which the units of the formula (1) or the preferred embodiments described above are present at 0.01 to 99.9 mol%, preferably 5 to 90 mol%, particularly preferably 20 to 80 mol%. Suitable and preferred comonomers which form the polymer backbone are selected from fluorenes (for example according to EP 842208 or WO 2000/022026), spirobifluorenes (for example according to EP 707020, EP 894107 or WO 2006/061181), para phenylenes (for example according to WO 92/18552), carbazoles (for example according to WO 2004/070772 or WO 2004/1 3468), thiophenes (for example according to EP 1028136), dihydrophenanthrenes (for example in accordance with WO 2005/014689), cisones (for example in accordance with WO 2005/040302), phenanthrenes (for example, according to WO 2005/014689), cis- and trans-indeno-fluorenes (for example according to WO 2004/041901 or WO 2004/113412). B. according to WO 2005/104264 or WO 2007/017066) or even more of these units. The polymers, oligomers and dendrimers may also contain other units, for example hole transport units, in particular those based on triarylamines, and / or electron transport units.

Yet another object of the present invention is a formulation containing a compound of the invention or a Oligomer, polymer or dendrimer according to the invention and at least one further compound. The further compound may for example be a solvent. Suitable solvents are, for example, toluene, xylenes, anisoles, methyl benzoate, dimethylanisoles, mesitylenes, tetralin, veratrol, THF, chlorobenzene or mixtures of these solvents. 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 complexes of the formula (1) and the above-mentioned preferred embodiments can be used in the electronic device as the active component. An electronic device is understood as meaning 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 option Guiding form of the invention are therefore organic Elektrolumineszenzvor- directions. Furthermore, the compounds according to the invention can be used for the production of singlet oxygen or in photocatalysis. The organic electroluminescent device includes cathode, anode and at least one emitting layer. In addition to these layers, they may also contain further layers, for example one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, charge generation layers and / or organic or inorganic p / n junctions. 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 can

or may include multiple emissive 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. Preference is given to three-layer systems, the three layers exhibiting blue, green and orange or red emission (for the basic structure see, for example, WO 2005/011013) or systems having more than three emitting layers. Also preferred are two-layer systems, in particular for lighting applications, wherein the two layers show blue and yellow emission. Many of the compounds according to the invention are currently suitable for use in two-component layer systems, as they show yellow emission. It may also be a hybrid system wherein one or more layers fluoresce and one or more other layers phosphoresce.

In a preferred embodiment of the invention, the organic electroluminescent device contains the compound according to formula (1) or the above-mentioned preferred embodiments as

emitting compound in one or more emitting layers.

When the compound of the formula (1) is used as an emitting compound in an emitting layer, it is preferably used in U.S.P.

 Combination with one or more matrix materials used. The mixture of the compound according to formula (1) and the matrix material contains between 0.1 and 99% by volume, preferably between 1 and 90% by volume, more preferably between 3 and 40% by volume, in particular between 5 and 15% by volume .-% of the compound according to formula (1) based on the total mixture of emitter and matrix material. Accordingly, the mixture contains between 99.9 and 1% by volume, preferably between 99 and 10% by volume, more preferably between 97 and 60% by volume, in particular between 95 and 85% by volume of the matrix material, based on the total mixture Emitter and matrix material.

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 tri-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-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, z. B. according to WO 2007/063754 or WO 2008/056746, indenocarbazole derivatives, for. B. according to WO 2010/136109 or WO 2011/000455, Azacarbazole, z. B. according to EP 1617710, EP 1617711, EP 1731584, JP 2005/347160, bipolar matrix materials, e.g. B. according to WO 2007/137725, silanes, z. B. according to WO 2005/111172, azaborole or boronic esters, z. B. according to WO 2006/117052, Diazasilolderivate, z. B. according to WO 2010/054729, Diazaphospholderivate, z. B. according to WO 2010/054730, triazine derivatives, z. B. according to WO

2010/015306, WO 2007/063754 or WO 2008/056746, zinc complexes, for. B. according to EP 652273 or WO 2009/062578, Dibenzofuranderivate, z. B. according to WO 2009/148015, or bridged carbazole derivatives, for. 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. As described in WO 2010/108579.

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, the complexes according to the invention of formula (1) can be used as a co-matrix for longer-wavelength emitting triplet emitters, for example for red emitting triplet emitters.

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 or as electron blocking material. Likewise, the complexes according to the invention can be used as matrix material for use 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 are suitable for this purpose, such as, for example, Ag, Pt or Au. On the other hand, metal / metal oxide electrodes (eg 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 (O-SC) 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 punched onto the anode Injection is applied, wherein suitable as p-dopants metal oxides, such as M0O ₃ or WO ₃ , or (per) fluorinated electron-poor aromatics. Further suitable p-dopants are HAT-CN (hexacyano-hexaazatriphenylene) or the compound NPD9 from Novaled. Such a layer simplifies the hole injection in materials with a low HOMO, 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 in vacuum sublimation are at an initial pressure of usually less than 10 ^-5 mbar, preferably below 10 ^{"vapor-deposited 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 (for example, BMS 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 (inkjet printing), are produced. For this purpose, soluble compounds are necessary, which are obtained for example by suitable substitution.

The organic electroluminescent device can also be manufactured 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.

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:

Organic electroluminescent devices containing compounds according to formula (1) as emitting materials have a good lifetime.

Organic electroluminescent devices comprising compounds according to formula (1) as emitting materials have a good efficiency. These advantages mentioned above 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 produce further inventive electronic devices from the descriptions without inventive step and thus carry out the invention in the entire claimed area.

Examples:

Unless stated otherwise, the following syntheses are carried out under an inert gas atmosphere in dried solvents. The metal complexes are additionally handled in the absence of light or under yellow light. The solvents and reagents may, for. B. from Sigma-ALDRICH or ABCR. The respective information in square brackets or the numbers given for individual compounds refer to the CAS numbers of the compounds known from the literature.

A: Synthesis of ligands L:

Example L1: 2- (1H-inden-2-yl) pyridines, L1

A mixture of 24.2 g (100 mmol) of indene-2-boronic acid pinacol ester [749869-98-5], 17.4 g (0 mmol) of 2-bromopyridine [109-04-6], 46.1 g

 (200 mmol) of tripotassium phosphate monohydrate, 300 ml of dioxane and 100 ml of water is combined with 821 mg (2 mmol) of S-phos and then with 249 mg (1 mmol) of palladium (II) acetate and heated under reflux for 16 h. To

Cooling is separated from the aqueous phase, the organic concentrated to dryness, the residue is taken up in 500 ml of ethyl acetate, the organic phase is washed three times with 200 ml of water, once with 200 ml saturated saline, dried over magnesium sulfate, filtered through a Celite bed from the desiccant and concentrated again to dryness. The oil thus obtained is freed from low boilers and nonvolatile secondary components by fractional Kugelrohr distillation twice. Yield: 10.8 g (56 mmol), 56%; Purity: approx. 99.5% after 1H NMR.

Analogously, the following compounds are shown. Solids by recrystallization and fractional sublimation (p is about 10 ^{~ 4} - ^{"10 5} mbar, T 160 - 240 ° C). Freed of low boilers and non-volatile secondary components oils are purified chromatographically fractionated Kugelrohr distilled or dried in a vacuum , around

 To remove low boilers.

B: Synthesis of metal complexes

1) Homoleptic tris-facial iridium complex:

 Variant A: tris-acetylacetonato-iridium (III) as iridium starting material

A mixture of 10 mmol Tris-acetylacetonato iridium (III) [15635-87-7] and 60 mmol of the ligand L and a glass-coated magnetic stirring bar will be under vacuum ( ^"5 mbar 10) melted in a thick-walled 50 ml glass vial. The vial is The mixture is tempered for the specified time at the indicated temperature, the molten mixture being stirred by means of a magnetic stirrer In order to avoid sublimation of the ligands to colder parts of the ampoule, the entire ampoule must have the indicated temperature Synthesis carried out in a stirred autoclave with glass insert. To

Cooling (CAUTION: the ampoules are usually under pressure!), The ampoule is opened, the sinter cake is with 100 g glass beads (3 mm diameter) in 100 ml of a suspending agent (the suspending agent is chosen so that the ligand is good, the metal complex but poor soluble in it, typical suspending agents being methanol,

Ethanol, dichloromethane, acetone, THF, ethyl acetate, toluene, etc.) for 3 h while mechanically digested. The fine suspension is decanted from the glass beads, the solid is filtered off with suction, washed with 50 ml of the suspending agent, and this is dried in vacuo. The dry solid is placed in a continuous hot extractor on a 3-5 cm high Alox bed (Alox, basic, activity level 1) and extracted with an extractant (amount of approximately 500 ml, the extractant is chosen such that the complex therein is in the Heat is good and poorly soluble in the cold, particularly suitable extractants are hydrocarbons such as toluene, xylenes, mesitylene, naphthalene, o-dichlorobenzene, halogenated aliphatic hydrocarbons are generally unsuitable because they may halogenate or decompose the complexes). After completion of the extraction, the extractant is concentrated in vacuo to about 100 ml. Metal complexes which have too good a solubility in the extractant are brought to crystallization by the dropwise addition of 200 ml of methanol. The solid of the suspensions thus obtained is filtered off with suction, washed once with about 50 ml of methanol and dried. After drying, the purity of the metal complex is determined by NMR and / or HPLC. If the purity is below 99.5%, the hot extraction step is repeated, the Alox bed being omitted from the 2nd extraction. If a purity of 99.5 - 99.9% is reached, the metal complex is tempered or sublimated. The annealing is carried out in high vacuum (p about 10 ^"6 mbar) in the temperature range of about 200-300 ° C, the sublimation is carried out in high vacuum (p about ^{10". 6} mbar) in the temperature range of about 230-400 ° C, wherein the sublimation is preferably carried out in the form of a fractional sublimation. Alternatively, complexes which are readily soluble in organic solvents can also be chromatographed on silica gel. Variant B: tris (2,2,6,6-tetramethyl-3,5-heptanedionato) iridium (III) as an iridium starting material

 Procedure analogous to variant A, wherein instead of 10 mmol tris acetyiacetonato iridium (III) [15635-87-7] 10 mmol tris (2,2,6,6-tetra-methyl-3,5-heptandionato) iridium [99581-86-9]. The use of this starting material is advantageous because the purity of the crude products obtained is often better than in variant A. In addition, the pressure build-up in the ampoule is often not so pronounced.

Variants C: Sodium [cis, trans-di-chloro (bis-acetylacetonato] iridate (III) as iridium starting material

 A mixture of 10 mmol of sodium [cis, trans-di-chloro (bis-acetyl-acetonato] iridate (III) [876296-21-8] and 60 mmol of the ligand in 50 ml of ethylene, propylene or diethylene glycol After cooling to 60 ° C., the mixture is diluted, with stirring, with 50 ml of ethanol, stirred for 1 h, filtered off with suction from the precipitated solid, washed three times with 30 ml of ethanol each time and then dried in vacuo Purification by hot extraction or chromatography and fractionated sublimation as described under A.

2) Iridium complexes of the type [Ir (L) ₂ Cl] ₂

 Option A:

A mixture of 24 mmol of the ligand, 10 mmol of iridium (III) chloride hydrate, 75 ml of 2-ethoxyethanol and 25 ml of water is refluxed with good stirring for 16 to 24 hours. If the ligand does not dissolve or does not dissolve completely in the solvent mixture under reflux, 1, 4-dioxane is added until a solution has formed. After cooling, the product is filtered off with suction from the precipitated solid, washed twice with ethanol / water (1: 1, v / v) and then dried in vacuo. That so obtained chloro-dimer of the formula [Ir (L) ₂ Cl] ₂ is further reacted without purification.

Variant B:

A mixture of 10 mmol of sodium bis-acetylacetonato-dichloro-iridate (III) [770720-50-8], 24 mmol of ligand L and a glass-coated magnetic stirrer core are melted under vacuum (10 ^"5 mbar) into a thick-walled 50 ml glass ampoule The ampoule is tempered for the specified time at the specified temperature, the molten mixture being stirred with the aid of a magnetic stirrer After cooling - CAUTION: the ampoules are usually under pressure! - the ampoule is opened, the sinter cake is mixed with 100 g glass beads (3 mm diameter) in 100 ml of the indicated suspending agent (the suspending agent is chosen so that the ligand is good, but the chloro-dimer of the formula [Ir (L) ₂ Cl] ₂ is poorly soluble in it; typical suspending agents are DCM, acetone , Ethyl acetate, toluene, etc.) for 3 h while mechanically digested, the fine suspension is decanted from the glass beads, the solid is sucked in [lr (L) ₂ Cl] ₂ , which still contains about 2 eq NaCl, nachfo called the crude chloro-dimer, and dried in vacuo. The crude chloro-dimer of the formula thus obtained

[Ir (L) ₂ Cl] ₂ is further reacted without purification.

3) iridium complexes of the type [Ir (L) ₂ (HOMe) ₂ ] OTf

A suspension of 5 mmol of the chloro-dimer [Ir (L) 2Cl] ₂ in 150 ml of dichloromethane is admixed with 5 ml of methanol and then with 10 mmol of silver (I) trifluoromethanesulfonate [2923-28-6], and 18 h stirred at room temperature. The precipitated silver (l) chloride is filtered off with suction through a bed of Celite, the filtrate is concentrated to dryness, the yellow residue is taken up in 30 ml of toluene or cyclohexane, filtered from the solid, washed with n-heptane and dried in vacuo , The product of the formula [Ir (L) ₂ (HOMe) ₂ ] OTf thus obtained is further reacted without purification.

4) Heteroleptic tris-O-metallated iridium complexes:

A mixture of 1 1 mmol of the ligand L, 10 mmol bis (methanol) bis [2- (2-pyridinyl-KN] phenyl-KC] iridium (III) trifluoromethanesulfonate [1215692-14-0] or bis (methanol) bis [2- (6-methyl-2-pyridinyl-KN] phenyl-KC] iridium (III) trifluoromethanesulfonate [1215692-29-7] or iridium complexes according to the invention of the type [Ir (L) ₂ (HOMe) ₂ OTf and 150 ml of ethanol are refluxed for 40 h and, after cooling, are filtered off with suction from the precipitated solid, washed three times with 30 ml of ethanol and dried in vacuo DCM, THF, toluene, n-heptane, cyclohexane) and subjected to fractional sublimation as described under 1) Variant A.

5) iridium complexes of the type Ir (L) ₂ L ^' containing non-o-metalated ligands L ^' :

A mixture of 25 mmol of the ligand L \ 10 mmol iridium-chloro-dimer [Ir (L) _{2 Cl} ] _2l 30 mmol of sodium bicarbonate, 100 ml of 2-ethoxyethanol and 30 ml of water is stirred at 90 ° C for 16 h. After cooling, the mixture is filtered off with suction from the precipitated solid, washed three times with 30 ml of ethanol each time and dried in vacuo. The crude product thus obtained is chromatographed or recrystallized on silica gel (solvent or mixtures thereof, eg DCM, THF, toluene, n-heptane, cyclohexane) and fractionated as described under 1) Variant A.

6) Platinum complexes of the type PtLL ^' containing non-O-metalated ligands L ^' :

 Preparation analogous to J. Brooks et al., Inorg. Chem. 2002, 41, 3055.

A mixture of 20 mmol of the ligand L, 10 mmol K ₂ PtCl ₄ , 75 ml of 2-ethoxyethanol and 25 ml of water is refluxed for 16 h. After cooling and addition of 100 ml of water is filtered off with suction from the precipitated solid, washed once with 30 ml of water and dried in vacuo. The resulting platinum-chloro-dimer of the formula [PtLClFE in 100 ml of 2-ethoxyethanol, 30 mmol of the ligands L ^' and 50 mmol of sodium carbonate are added, the reaction mixture is stirred for 16 hours at 100 ° C. and then concentrated to dryness in vacuo one. The crude product thus obtained is chromatographed on silica gel (solvent or mixtures thereof, eg DCM, THF, toluene, n-heptane, cyclohexane) or

recrystallized, and as described under 1) variant A fractionally sublimed.

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, based on the circumstances described here

(Layer thickness variation, materials used) is adjusted. The following examples introduce the results of different OLEDs. Glass plates with structured ITO (indium tin oxide) form the substrates onto 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 Blocking 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.

For the vacuum-processed OLEDs, 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 like

M1: M2: lr (L1) ₃ (55%: 35%: 10%) means that the material M1 in a volume fraction of 55%, M2 in a proportion of 35% and lr (L1) ₃ in a proportion of 10% is present in the layer. Analog can also the

Electron transport layer 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 3. 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). For selected tests, the service life is determined. The life is defined as the time after which the luminance has dropped to a certain level from a certain starting luminance. The term LD50 means that the stated lifetime is the time at which the luminance has fallen to 50% of the starting luminance, ie from 1000 cd / m ² to 500 cd / m ² . Depending on the emission color, different starting brightnesses were selected. The values for the lifetime can be converted to an indication for other starting luminance densities with the aid of conversion formulas known to the person skilled in the art. Here, the life for a starting luminous flux of 1000 cd / m ^{2 is} a common statement. Use of compounds according to the invention as emitter materials in phosphorescent OLEDs

 The compounds according to the invention can be used inter alia as phosphorescent emitter materials in the emission layer in OLEDs. The results of the OLEDs are summarized in Table 2.

Table 1: Structure of the OLED

HTL2 EML HBL ETL

Ex.

 Thickness Thickness Thickness

M1: M2: lr (L1) ₃

 HTM ΕΤΜ1 ΈΤΜ2

 HBM

D-Ir (L1) ₃ (45%: 45%: 10%) (50%: 50%)

 70 nm 10 nm

 25 nm 45 nm

M1: M2: lr (L2) ₃

 HTM ETM1: ETM2

D-lr (L2) ₃ (45%: 45%: 10%) -

 70 nm (50%: 50%)

 25 nm 45 nm

M1: M2: lr (L3) ₃

 HTM ΕΤΜ1 ΈΤΜ2

D-lr (L3) ₃ (45%: 45%: 10%) -

 70 nm (50%: 50%)

 25 nm 45 nm

M1: M2: lr (L4) ₃

 HTM ETM1: ETM2

D-lr (L4) ₃ (45%: 45%: 10%) -

 70 nm (50%: 50%)

 25 nm 45 nm

M1: M2: lr (L5) ₃

 HTM ΕΤΜ1 ΈΤΜ2

D-lr (L5) ₃ (45%: 45%: 10%) -

 70 nm (50%: 50%)

 25 nm 45 nm

M1: M2: lr (L6) ₃

 HTM ΕΤΜ1 ΈΤΜ2

D-lr (L6) ₃ (45%: 45%: 10%) -

 70 nm (50%: 50%)

 25 nm 45 nm

M1: M2: lr (L7) ₃

 HTM ΕΤΜ1 ΈΤΜ2

D-lr (L7) ₃ (45%: 45%: 10%) - (50%: 50%)

 70 nm

 25 nm 45 nm

M1: M2: lr (L8) ₃

 HTM ΕΤΜ1 ΈΤΜ2

D-lr (L8) ₃ (45%: 45%: 10%) - (50%: 50%)

 70 nm

25 nm 45 nm ETM1: ETM2

HTM M1: M2: lr (L9) ₃

D-lr (L9) ₃ (45%: 45%: 10%) - (50%: 50%)

 70 nm

 25 nm 45 nm

M1: M2: lr500 ΕΤΜ1ΈΤΜ2

HTM

 D-Ir500 (45%: 45%: 10%) - (50%: 50%)

 70 nm

 25 nm 45 nm

M1: M2: lr501 ΕΤΜ1ΈΤΜ2

HTM

 D-Ir501 (45%: 45%: 10%) - (50%: 50%)

 70 nm

 25 nm 45 nm

M1: M2: lr502

 HTM ΕΤΜ1ΈΤΜ2

D-Ir502 (45%: 45%: 10%) - (50%: 50%)

 70 nm

 25 nm 45 nm

M1: M2: lr503 ΕΤΜ1ΈΤΜ2

HTM

 D-Ir503 (45%: 45%: 10%) - (50%: 50%)

 70 nm

 25 nm 45 nm

M1: M2: lr504 ΕΤΜ ΈΤΜ2

HTM

 D-Ir504 (45%: 45%: 10%) - (50%: 50%)

 70 nm

 25 nm 45 nm

M1: M2: lr505 ΕΤΜ1ΈΤΜ2

HTM

 D-Ir505 (45%: 45%: 10%) - (50%: 50%)

 70 nm

 25 nm 45 nm

M1: M2: lr506 ΕΤΜ1ΈΤΜ2

HTM

 D-Ir506 (45%: 45%: 10%) - (50%: 50%)

 70 nm

 25 nm 45 nm

M1: M2: lr507 ΕΤΜ1.ΈΤΜ2

HTM

 D-Ir507 (45%: 45%: 10%) - (50%: 50%)

 70 nm

 25 nm 45 nm

M1: M2: lr700 ΕΤΜ1ΈΤΜ2

HTM

 D-Ir700 (45%: 45%: 10%) - (50%: 50%)

 70 nm

 25 nm 45 nm

M1: M2: lr701 ΕΤΜ1ΈΤΜ2

HTM

 D-Ir701 (45%: 45%: 10%) -

 70 nm (50%: 50%)

25 nm 45 nm M1: M2: Ir702 ETM1: ETM2

HTM

 D-Ir702 (45%: 45%: 10%) - (50%: 50%)

 70 nm

 25 nm 45 nm

M1: M2: lr703 ΕΤΜ1 ΈΤΜ2

HTM

 D-Ir703 (45%: 45%: 10%) - (50%: 50%)

 70 nm

 25 nm 45 nm

M1: M2: lr704 ETM1: ETM2

HTM

 D-Ir704 (45%: 45%: 10%) - (50%: 50%)

 70 nm

 25 nm 45 nm

M1: M2: Pt001 ΕΤΜ1 ΈΤΜ2

HTM

 001 (65%: 25%: 10%) - (50%: 50%)

 70 nm

 25 nm 45 nm

M1: M2: Pt002 ΕΤΜ1 ΈΤΜ2

HTM

 Pt002 (55%: 35%: 10%) - (50%: 50%)

 70 nm

 25 nm 45 nm

M1: M2: Pt003 ΕΤΜ1.ΈΤΜ2

HTM

 Pt003 (45%: 45%: 10%) - (50%: 50%)

 70 nm

 25 nm 45 nm

Table 2: Results of the vacuum-processed OLEDs

 EQE (%) Voltage (V) CIE x / y LD50 (h)

Ex.

1000 cd / m ² 1000 cd / m ² 1000 cd / m ² 1000 cd / m ²

D-lr (L1) ₃ 14.7 3.0 0.63 / 0.36 18000

D-lr (L2) ₃ 15.3 3.0 0.62 / 0.38 -

D-lr (L3) ₃ 6.0 3.1 0.53 / 0.45 -

D-lr (L4) ₃ 13.9 2.9 0.67 / 0.33 43000

D-lr (L5) ₃ 14.8 3.0 0.51 / 0.48 -

D-lr (L6) ₃ 17.9 3.0 0.66 / 0.34 150000

D-lr (L7) ₃ 18.5 2.8 0.66 / 0.34 135000

D-lr (L8) ₃ 18.6 2.9 0.66 / 0.34 160000

D-lr (L9) ₃ 17.8 2.9 0.69 / 0.31 220000

D-Ir500 17.9 2.8 0.62 / 0.38 180000

D-Ir501 18.0 2.9 0.63 / 0.37 -

D-Ir502 15.7 2.8 0.68 / 0.32 230000

D-Ir503 17.3 2.9 0.64 / 0.36 175000

D-Ir504 15.9 2.9 0.69 / 0.31 210000

D-Ir505 18.6 2.9 0.66 / 0.34 190000

D-Ir506 19.2 3.0 0.65 / 0.34 270000

D-Ir507 16.8 2.9 0.69 / 0.31 240000 D-Ir700 16.3 3.2 0.66 / 0.34 -

D-Ir701 15.8 3.1 0.68 / 0.32 155000

D-Ir702 16.5 3.2 0.66 / 0.34 -

D-Ir703 16.7 3.3 0.66 / 0.34 -

D-Ir704 15.6 3.2 0.68 / 0.32 -

Pt001 12.4 3.6 0.66 / 0.34 -

Pt002 13.0 3.5 0.66 / 0.34 60000

Pt003 14.1 3.5 0.67 / 0.33 -

Claims

 claims

1. compound according to formula (1),

M (L) _n (L ') _m formula (1) containing a partial structure M (L) _n of formula (2), (3) or (4):

 Formula (2) Formula (3) Formula (4) where for the symbols and indices used: M is a transition metal;

CyN is a heteroaryl group having 5 to 18 aromatic ring atoms, which coordinates to M via a nitrogen atom and which may be substituted by one or more radicals R;

A is the same or different CR ₂ , C (= 0), C (= NR) or BR at each occurrence;

Z is the same or different CR or N at each occurrence; or the two adjacent groups Z in formula (2) or formula (3) stand for a group of the following formula (5),

Y Y

 \\ //

 Y-Y

Formula (5) the dashed bonds indicating the linkage of this moiety in the structure of formula (2) and (3), respectively; is the same or different at each occurrence CR or N; is identical or different at each occurrence H, D, F, Cl, Br, I, N (R ¹ ) ₂ , CN, NO _2> OH, COOH, C (= O) N (R ¹ ) ₂ , Si (R ¹ ) ₃ , B (OR ¹ ) ₂ , C (= 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 having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms each of which may be substituted with one or more R ¹ radicals, wherein one or more non-adjacent CH ₂ groups are represented by R ¹ C = CR ¹ , C = C, Si (R) ₂ , C = O, NR ¹ , O , S or CONR ¹ may be replaced and wherein one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, each by one or more a plurality of R ¹ may be substituted, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, by one or more radicals R ¹ may be substituted, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms which may be substituted by one or more radicals R ¹ , or a Diarylamino-, Diheteroarylaminogruppe or Arylheteroarylamino- group having 10 to 40 aromatic ring atoms which may be substituted by one or more radicals R ¹ ; two or more radicals R may also together form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system; is identical or different at each occurrence H, D, F, Cl, Br, I, N (R ² ) ₂ , CN, NO ₂ , Si (R ² ) ₃ , B (OR ² ) ₂ , C (= O) R ² , P (= O) (R ² ) ₂ ,

S (OO) R ² , S (OO) ₂ R ² , OSO ₂ R ² , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C Atoms or a branched one or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, each of which may be substituted with one or more R ² radicals, wherein one or more non-adjacent CH ₂ groups is represented by R ² C = CR ² , C = C, Si (R) ₂ , C = O, NR ² , O, S or CONR ² may be replaced and wherein one or more H atoms may be replaced by D, 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 or heteroaryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R ² may, or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms which may be substituted by one or more radicals R ² , or a Diarylaminogruppe, Diheteroarylamino- group or Arylheteroarylaminogruppe having 10 to 40 aromatic ring atoms, which by one or more radicals R ² may be substituted; two or more adjacent radicals R ¹ with one another or R ¹ with R can form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic 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 ring system;

L 'is the same or different at each occurrence a coligand; n is 1, 2 or 3; m is 0, 1, 2, 3 or 4; several ligands L can be used with each other or L with L 'via a single bond or a bivalent or trivalent bridge. be linked and thus span a tridentates, tetradentates, pentadentates or hexadentates ligand system; Furthermore, a substituent R can additionally coordinate to the metal.

A compound according to claim 1, characterized in that M is selected from the group consisting of chromium, molybdenum,

 Tungsten, rhenium, ruthenium, osmium, rhodium, iridium, nickel, palladium, platinum, copper, silver and gold.

Compound according to Claim 1 or 2, characterized in that the substructure M (L) _{n represents} a structure of the formula (6a) or (7a),

 Formula (6a) Formula (7a) wherein the symbols and indices used have the meanings given in claim 1.

4. A compound according to one or more of claims 1 to 3,

characterized in that A is CR ₂ , wherein R is the same or different at each occurrence selected from the group consisting of a straight-chain alkyl group having 1 to 20 C-atoms or a branched or cyclic alkyl group having 3 to 20 C-atoms, the each may be substituted with one or more radicals R ¹ , wherein one or more non-adjacent CH ₂ groups is represented by R ¹ C = CR ¹ , C ¹ -C ⁴ , Si (R ¹ ) ₂ , C = O, NR ¹ , O, S or CONR ¹ may be replaced and wherein one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, the each may be substituted by one or more radicals R ¹ , or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R; In this case, the radicals R can also form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another.

Compound according to one or more of Claims 1 to 4, characterized in that CyN is selected from the groups of the formulas (CyN-1) to (CyN-7) which are each bonded to the cyclopentadiene or indene at the position indicated by # ligands and coordinates to the metal at the position indicated by ^* ,

(CyD-3)

wherein R has the meanings mentioned in claim 1 and furthermore:

X is the same or different CR or N at each occurrence;

W is the same or different NR, O or S at each occurrence.

A compound according to one or more of claims 1 to 5, characterized in that CyN is selected from the groups of the following formulas (CyN-1a) to (CyN-7a), each at the by # binds to the cyclopentadiene or indene of the ligand and coordinates to the metal at the position indicated by ^* ,

wherein the symbols used have the meanings given in claims 1 and 5.

7. A compound according to one or more of claims 1 to 6,

 characterized in that two adjacent radicals R together form an aliphatic cycle containing no acidic benzylic protons, and / or that two or more radicals R which are bonded to CyN and to A and Z, respectively, form a ring with each other.

8. A compound according to one or more of claims 1 to 7,

 characterized in that L 'is selected from the group consisting of carbon monoxide, nitrogen monoxide, alkyl cyanides, aryl cyanides, alkyl isocyanides, aryl isocyanides, amines, phosphines, phosphites, arsines, stibines, nitrogen-containing heterocycles,

Carbenes, hydride, interpreting, the halides F ^~ CP, ΒΓ and Γ, alkylacetylidene, arylacetylidene, cyanide, cyanate, isocyanate, thiocyanate, isothiocyanate, aliphatic or aromatic alcoholates, aliphatic or aromatic thioalcoholates, amides, carboxylates, aryl groups, O ^{2 "} , S ^{2 "} , carbides, nitrenes, diamines, imines,

Diimines, diphosphines, 1,3-diketonates derived from 1,3-diketones, 3-ketonates derived from 3-ketoesters, carboxylates derived from aminocarboxylic acids, salicyliminates derived from salicylimines, dialcoholates, dithiolates, borates of nitrogenous heterocycles, bidentate monoanionic, neutral or

dianionic ligands which form with the metal a cyclometallated five-membered or six-membered ring with at least one metal-carbon bond, in particular a cyclometallated five-membered ring, η ⁵ -cyclopentadienyl, r | ^5- pentamethylcyclopentadienyl, η ⁶ -ββηζοΙ and η ⁷ -cycloheptatrienyl.

A process for preparing a compound according to one or more of claims 1 to 8 by reacting the free ligands L and optionally L 'with metal alcoholates of the formula (73), with metal ketoketones of the formula (74), with metal halides of the formula (75), with dimers Metal complexes of the formula (76) or with metal complexes of the formula (77) or with metal compounds, in particular iridium compounds which contain both alkoxide and / or

 Wear halide and / or hydroxy as well as ketoketonate radicals,

M (OR) _n MHal _n

 Formula (73) Formula (74) Formula (75)

 (Anion)

 Formula (76) Formula (77) wherein the symbols M, m, n and R have the meanings given in claim 1, Hai = F, Cl, Br or I, L "is an alcohol or a nitrile and (anion) is a non-coordinating anion.

10. oligomer, polymer or dendrimer comprising one or more of the compounds according to one or more of claims 1 to 8, wherein one or more bonds of the invention

 Compound to the polymer, oligomer or dendrimer are present.

11. Use of a compound according to one or more of

 Claims 1 to 8 or an oligomer, polymer or dendrimer according to claim 0 in the electronic device or to

 Generation of singlet oxygen or in photocatalysis.

12. Electronic device comprising at least one compound according to one or more of claims 1 to 8 or at least one oligomer, polymer or dendrimer according to claim 10, 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.

13. An electronic device according to claim 12, which is an organic electroluminescent device, characterized in that the compound according to one or more of

 Claims 1 to 8 or the oligomer, polymer or dendrimer according to claim 10 is present as an emitting compound in one or more emitting layers, in particular used in combination with one or more matrix materials.

14. Electronic device according to claim 13, characterized in that the matrix material is selected from the group consisting of ketones, phosphine oxides, sulfoxides, sulfones, triarylamines, carbazole derivatives, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazoles, bipolar matrix materials, silanes, azaboroles, boron esters, Diazasilol derivatives, diazaphosphole derivatives, triazine derivatives, zinc complexes, dibenzofuran derivatives or bridged carbazole derivatives.