Binuclear and trinuclear metal complexes containing two interconnected tripodal hexadentate ligands for use in electroluminescent devices

Abstract

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

Description

[0001] The present invention relates to dinuclear and trinuclear metal complexes which are suitable as emitters in organic electroluminescent devices.

[0002] According to the prior art, triplet emitters for use in phosphorescent organic electroluminescent devices (OLEDs) are in particular bis-ortho-metalated and tris-ortho-metalated iridium complexes containing aromatic ligands, wherein the ligands are bound to the metal via a negatively charged carbon atom and a neutral nitrogen atom or via a negatively charged carbon atom and a neutral carbene carbon atom. Examples of such complexes are tris(phenylpyridyl)iridium(III) and derivatives thereof, wherein the ligands used are for example 1-phenylisoquinoline or 3-phenylisoquinoline, 2-phenylquinoline or phenylcarbene. These iridium complexes generally have a rather long luminescence lifetime, for example 1.6 ps in dichloromethane at a photoluminescence quantum yield of 90 ± 5% in the case of tris(phenylpyridyl)iridium(III) (Inorg. Chem. 2010, 9290). However, for use in OLEDs, a short luminescence lifetime is required in order to be able to operate the OLEDs at high brightness with low roll-off properties. There is also a need to improve the efficiency of red phosphorescent emitters. Due to the low triplet energy level T1, the photoluminescence quantum yield in conventional red phosphorescent emitters is generally significantly lower than the theoretically possible value, because in the case of a low T1, the non-radiative channels also play a greater role, in particular when the complexes have a long luminescence lifetime. Here, an improvement is required by increasing the radiation rate, which in turn can be achieved by reducing the photoluminescence lifetime.

[0003] Improvements in the stability of the complexes have been achieved by using polydentate ligands, as described for example in WO 2004 / 081017, US 7,332,232 and WO 2016 / 124304. Even if these complexes show advantages compared to complexes having the same ligand structure, but whose individual ligands are not polydentate, there is still a need for improvement. Thus, even in the case of complexes having polydentate ligands, there is still a need for improvement with regard to the performance, in particular with regard to the efficiency, the voltage and / or the lifetime, when used in organic electroluminescent devices.

[0004] It was therefore an object of the present invention to provide novel metal complexes which are suitable as emitters for use in OLEDs. In particular, it was an object to provide emitters which exhibit improved performance with regard to the photoluminescence quantum yield and / or the luminescence lifetime, and / or which exhibit improved performance with regard to the efficiency, the operating voltage and / or the lifetime, when used in OLEDs.

[0005] Surprisingly, it has been found that the dinuclear and trinuclear rhodium and iridium complexes described below exhibit a significant improvement in photophysical properties compared to the corresponding mononuclear complexes, thus also leading to improved performance when used in organic electroluminescent devices. In particular, the compounds according to the present application have an improved photoluminescence quantum yield and a significantly reduced luminescence lifetime. The short luminescence lifetime leads to an improved roll-off behavior of the organic electroluminescent device. The present application relates to these complexes and to organic electroluminescent devices containing these complexes.

[0006] The present application therefore relates to a compound of the following formula (1) or (2),

[0007]

[0008] where the following applies to the symbols and indices used:

[0009] M is, on each occurrence identically or differently, iridium or rhodium;

[0010] Q is an aryl or heteroaryl group having 6 to 10 aromatic ring atoms, which group is in each case identically or differently coordinated to each of the two or three M via a carbon or nitrogen atom, and which group can be substituted by one or more radicals R; here the coordinating atoms in Q are not bonded to each other in the ortho position;

[0011] D is, on each occurrence identically or differently, C or N;

[0012] X is, on each occurrence identically or differently, CR or N;

[0013] p is 0 or 1 ;

[0014] V is, on each occurrence identically or differently, a group of the following formula (3) or (4),

[0015]

[0016] where one of the dotted bonds denotes the bond to the corresponding 6-membered aryl or heteroaryl ring group depicted in formula (1) or (2), and the other two dotted bonds each denote a bond to the partial ligand L;

[0017] L is, on each occurrence identically or differently, a bidentate monanionic partial ligand;

[0018] X 1 is, on each occurrence identically or differently, CR or N;

[0019] A 1 is, on each occurrence identically or differently, C(R)2 or O;

[0020] A 2CR, P(=O), B or SiR, with the proviso that, for A 2 = P(=O), B or SiR, the symbol A 1 represents O and is bound to this A 2 the symbol A bound thereto does not represent -C(=O)-NR'- or -C(=O)-O-;

[0021] A is on each occurrence, identically or differently, -CR=CR-, -C(=O)-NR'-, -C(=O)-O-, -CR2-CR2-, -CR2-O- or a radical of the following formula (5),

[0022]

[0023] wherein the dotted bond denotes the position of the bond from the bidentate ligand L or from the corresponding 6-membered aryl or heteroaryl ring radical depicted in formula (1) or (2) to the structure, and * denotes the position of the attachment of the unit of formula (5) to the central cyclic radical (i.e. the radical explicitly shown in formula (3) or (4));

[0024] X 2 is on each occurrence, identically or differently, CR or N, or two adjacent radicals X 2 together represent NR, O or S, such that a five-membered ring is formed, and the remaining X 2 is on each occurrence, identically or differently, CR or N; or if one of the radicals X 3 in the ring represents N, then two adjacent radicals X 2 together represent CR or N, such that a five-membered ring is formed; with the proviso that at most two adjacent radicals X 2 represent N;

[0025] X 3 is on each occurrence C, or one radical X 3 in the same ring represents N and the other radical X 3 represents C; with the proviso that, if one of the radicals X 3 in the ring represents N, then two adjacent radicals X 2 together represent CR or N;

[0026] R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R 1 )2, CN, NO2, OR 1 , SR 1 , COOH, C(=O)N(R 1 )2, Si(R 1 )3, B(OR 1 )2, C(=O)R 1 , P(=O)(R1 )2, S(=O)R 1 , S(=O)2R 1 , OSO2R 1 , COO(cation), SO3(cation), OSO3(cation), OPO3(cation)2, O(cation), N(R 1 )3(anion), P(R 1 )3(anion), 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, it being possible for the alkyl, alkenyl or alkynyl groups in each case to be substituted by one or more radicals R 1 , in which one or more non-adjacent CH2groups can be replaced by Si(R 1 )2, C=O, NR 1 , O, S or CONR 1 ; or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may, in each case, be substituted by one or more radicals R 1 ; it also being possible for two radicals R to form a ring system with one another;

[0027] R' on each occurrence, identically or differently, is H, D, a straight-chain alkyl group having 1 to 20 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, it being possible for the alkyl groups in each case to be substituted by one or more radicals R 1 and in which one or more non-adjacent CH2groups can be replaced by Si(R 1 )2; or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which may, in each case, be substituted by one or more radicals R 1 ;

[0028] R 1 on each occurrence, identically or differently, is H, D, F, Cl, Br, I, N(R 2 )2, CN, NO2, OR 2 , SR 2 , Si(R 2 )3, B(OR 2 )2, C(=O)R 2 , P(=O)(R 2 )2, S(=O)R 2 , S(=O)2R 2 , OSO2R 2 , COO(cation), SO3(cation), OSO3(cation), OPO3(cation)2, O(cation), N(R 2 )3(anion), P(R2 ) 3 (anion), 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 can in each case be substituted by one or more radicals R 2 , wherein one or more non-adjacent CH2 groups can be replaced by Si(R 2 )2, C=0, NR 2 , O, S or CONR 2 ; or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which can in each case be substituted by one or more radicals R 2 ; here two or more radicals R 1 may form a ring system with one another;

[0029] R 2 is on each occurrence, identically or differently, H, D, F, or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in particular a hydrocarbon radical, wherein one or more H atoms can also be replaced by F;

[0030] the cation is on each occurrence, identically or differently, selected from the group consisting of a proton, a deuteron, an alkali metal ion, an alkaline earth metal ion, an ammonium, a tetraalkylammonium and a tetraalkyl phosphonium ion;

[0031] the anion is on each occurrence, identically or differently, selected from the group consisting of a halide ion, a carboxylate ion R 2 -COO - , a cyanide ion, a cyanate ion, an isocyanate ion, a thiocyanate ion, an isothiocyanate ion, a hydroxide ion, BF4 - , PF6 - , B(C6F5)4 - , a carbonate ion and a sulfonate ion.

[0032] If two radicals R or R 1 form a ring system with one another, this can be a monocyclic or polycyclic aliphatic, heteroaliphatic, aromatic or heteroaromatic ring system. The radicals forming a ring system with one another can be adjacent, i.e. these radicals are bonded to the same carbon atom or to carbon atoms which are directly bonded to one another, or they can be remote from one another. In the case of radicals which are bonded to one another directly bonded carbon atoms or to the same carbon atom, this type of ring formation is preferred.

[0033] For the purposes of the present specification, the expression that two or more radicals can form a ring with one another is intended to be understood as meaning, in particular, that the two radicals are connected to one another by a chemical bond which formally eliminates two hydrogen atoms. This is illustrated by the following scheme:

[0034]

[0035] However, the above expressions are furthermore intended to be understood to mean that, in the case where one of the two radicals represents hydrogen, the second radical is bonded at the position where the hydrogen atom is bonded, thus forming a ring. This is intended to be illustrated by the following scheme:

[0036]

[0037] The formation of the aromatic ring system is intended to be illustrated by the following scheme:

[0038]

[0039] An aryl group in the sense of the present application contains 6 to 40 C atoms; a heteroaryl group in the sense of the present application contains 2 to 40 C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O and / or S. An aryl group or heteroaryl group here means a simple aromatic ring, i.e. benzene, or a simple heteroaromatic ring, e.g. pyridine, pyrimidine, thiophene, etc., or a fused aryl or heteroaryl group, e.g. naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc.

[0040] An aromatic ring system in the sense of the present application contains 6 to 40 C atoms in the ring system. A heteroaromatic ring system in the sense of the present application contains 1 to 40 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 heteroatom is preferably selected from N, O and / or S. An aromatic or heteroaromatic ring system in the sense of the present application is intended to mean a system which does not necessarily contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups can also be interrupted by non-aromatic units, preferably less than 10% of the non-H atoms, which are, for example, C, N or O atoms or carbonyl groups. Thus, for example, systems such as 9,9'-spirobifluorene, 9,9-dialkylfluorene, triarylamine, diaryl ether, stilbene, etc., are also intended to be regarded as aromatic ring systems in the sense of the present application, as are systems in which two or more aryl groups are interrupted by, for example, linear or cyclic alkyl groups or by silyl groups. Furthermore, systems in which two or more aryl or heteroaryl groups are bonded directly to one another, such as biphenyl, terphenyl, quaterphenyl or bipyridine, are likewise intended to be regarded as aromatic or heteroaromatic ring systems. The aromatic or heteroaromatic ring system is preferably a system in which two or more aryl or heteroaryl groups are directly connected to one another via single bonds, or is fluorene, spirobifluorene or another aryl or heteroaryl group on which an optionally substituted indene group has been fused, for example indenocarbazole.

[0041] A cyclic alkyl group in the sense of the present application means a monocyclic, bicyclic or polycyclic group.

[0042] For the purposes of this invention, individual H atoms or CH2 groups may be replaced by the aforementioned groups at C1 to C2. 20 Alkyl groups refer to groups such as methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, sec-pentyl, tert-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, sec-hexyl, tert-hexyl, 2-hexyl, 3-hexyl, neohexyl, 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 1,1-dimethyl-n-octyl-1-yl, 1,1-dimethyl-n-decane-1-yl, 1,1-dimethyl-n-tetradecane-1-yl, 1,1-dimethyl-n-hexadecane-1-yl, 1,1-dimethyl-n-octadecane-1-yl, 1,1-diethyl-n-hexyl-1-yl, 1,1-diethyl-n-heptane-1-yl, 1,1-diethyl-n-octyl-1-yl, 1,1-diethyl- n-Dec-1-yl, 1,1-diethyl-n-dodecane-1-yl, 1,1-diethyl-n-tetradecane-1-yl, 1,1-diethyl-n-hexadecane-1-yl, 1,1-diethyl-n-octadecane-1-yl, 1-(n-propyl)cyclohexyl-1-yl, 1-(n-butyl)cyclohexyl-1-yl, 1-(n-hexyl)cyclohexyl-1-yl, 1-(n-octyl)cyclohexyl-1-yl, and 1-(n-decyl)cyclohexyl-1-yl. Alkenyl groups refer to, for example, vinyl, propynyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, or cyclooctadienyl. Alkynyl groups refer to, for example, ethynyl, propynyl, butynyl, penynyl, hexynyl, heptenyl, or octynyl. C1 to C 20 Alkoxy groups, such as OR 1 OR 2 The substances present refer to, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, or 2-methylbutoxy.

[0043] Aromatic or heteroaromatic ring systems having 5-40 aromatic ring atoms, which in each case can be substituted by the aforementioned groups and can be linked to the aromatic or heteroaromatic ring system via any desired position, refer to groups derived, for example, from substances such as: benzene, naphthalene, anthracene, benzo[a]anthracene, phenanthrene, benzo[a]phenanthrene, pyrene, etc. , perylene, fluoranthene, benzofluoranthene, tetracene, pentacene, benzopyrene, biphenyl, biphenylidene, terphenyl, terphenylidene, fluorene, spirobifluorene, dihydrouin, dihydropyrene, tetrahydropyrene, cis or trans indenofluorene, cis or trans monobenzoindenofluorene, cis or trans dibenzoindenofluorene, triindene, iso-triindene, spiro-triindene, spiro-iso-triindene, 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, benzoimidazole, naphthoimidazole, phenanthroimidazole, pyridinoimidazole, pyrazinoimidazole, quinoxalinoimidazole, , pyrazole, indazole, imidazole, benzoimidazole, naphthoimidazole, phenanthroimidazole, pyridinoimidazole, pyrazinoimidazole, quinoxalinoimidazole, , pyrazole, indazole, imidazole, benzoimidazole, naphthoimidazole, phenanthroimidazole, pyridinoimidazole, pyrazinoimidazole, quinoxalinoimidazole, , pyrazole, indazole, imidazole, benzoimidazole, naphthoimidazole, phenanthroimidazole, pyridinoimidazole, pyrazinoimidazole, quinoxalinoimidazole, , pyrazole, indazole, imidazole, benzoimidazole, naphthoimidazole, phenanthroimidazole, pyridinoimidazole, pyrazinoimidazole, quinoxalinoimidazole, , pyrazole, indazole, imidazole, benzoimidazole, naphthoimidazole, phenanthroimidazole, pyridinoimidazole, pyrazinoimidazole, quinoxalinoimidazole, , pyrazole, indazole, imidazole, benzoimidazole, naphthoimidazole, phenanthroimidazole, pyridinoimidazole, pyrazinoimidazole, quinoxalinoimidazole, , pyrazole, indazole, imidazole, benzoimidazole, naphthoimidazole, phenanthroimidazole, pyridinoimidazole, pyrazinoimidazole, quinoxalinoimidazole, , pyrazole, indazole, imidazole, benzoimidazole, naphthoimidazole, phenanthroimidazole, pyridinoimidazole, pyrazinoimidazole, quinoxalinoimidazole, , pyrazole, indazole, imidazole, benzoimidazole, naphthoimidazole, phenanthroimidazole, pyridinoimidazole, pyrazinoimidazole, quinoxalinoimidazole, , pyrazole, indazole, imidazole, benzoimidazole, naphthoimidazole, phenanthroimidazole, pyridinoimidazole, pyrazinoimidazole, quinoxalinoimidazole, , pyrazole, indazole, imidazole, benzoimidazole, naphthoimidazole, phenanthroimidazole, pyridinoimidazole, pyrazinoimidazole, quinoxalinoimidazole, , pyrazole, indazole, imidazole, benzoimidazole, naphthoimidazole, phenanthroimidazole, pyridinoimidazole, pyrazinoimidazole, quinoxalinoimidazole,

[0044] To further illustrate the compounds, a simple structure of Formula (1) is drawn as a whole and explained below:

[0045]

[0046] In this structure, Q represents a pyrimidine group, wherein the pyrimidine is in each case coordinated to one of the two metals M via each of the two nitrogen atoms. The two phenyl groups, which correspond to the two six-membered aryl or heteroaryl ring groups in formula (1) and are in each case coordinated to one of the two metals M via a carbon atom, are bonded to the pyrimidine. In the above illustrative structure, in each case a group of formula (3) is bonded to each of the two phenyl groups, i.e. V in this structure represents a group of formula (3). The central ring therein is in each case a phenyl group and the three groups A each represent -HC=CH-, i.e. a cis-alkenyl group. In each case, two partial ligands L, which in the above structure each represent a phenylpyridine, are also bonded to this group of formula (3). Thus, each of the two metals M in the above structure is in each case coordinated to two phenylpyridine ligands and one phenylpyrimidine ligand, wherein the pyrimidine group of the phenylpyrimidine is coordinated to both metals M. The partial ligands here are each connected by a group of formula (3) to form a poly-pod system.

[0047] The term "bidentate partial ligand" for L in the sense of the present application means that this unit would be a bidentate ligand if the group V, i.e. the group of formula (3) or (4), were not present. However, the formal elimination of a hydrogen atom on this bidentate ligand and the connection with the group V, i.e. the group of formula (3) or (4), means that this is not a separate ligand, but rather a part of a twelve-dentate ligand (i.e. a ligand with a total of 12 coordination sites) formed in this way with p = 0, and thus the term "partial ligand" is used here. Correspondingly, for p = 1, the ligand has 18 coordination sites.

[0048] The bond from the ligand to the metal M can be a coordinate bond or a covalent bond, or the covalent content of the bond can vary depending on the ligand. If the present application refers to a ligand or partial ligand being coordinated or bonded to M, this means in the sense of the present application any type of bonding of the ligand or partial ligand to M, independent of the covalent content of the bond.

[0049] The compounds according to the application are preferably uncharged, i.e. they are electrically neutral. This is achieved by Rh or Ir being in each case in the oxidation state +III. Each metal is then coordinated by three mononegative bidentate partial ligands, so that the partial ligands compensate the charge of the complex metal atom.

[0050] As mentioned above, the two metals M in the compounds according to the application can be the same or different and are preferably in the oxidation state +III. Thus, for p = 0, the combinations Ir / Ir, Ir / Rh and Rh / Rh are all feasible. In a preferred embodiment of the application, both metals M represent Ir(III). Similarly, for p = 1, the combinations Ir / Ir / Ir, Ir / Ir / Rh, Ir / Rh / Rh and Rh / Rh / Rh are all feasible, and preferably all three metals M represent Ir(III).

[0051] In a preferred embodiment of the application, the compounds of the formulae (1 ) and (2) are selected from the compounds of the following formulae (1 a) and (2a),

[0052]

[0053] wherein the group R explicitly drawn in ortho position of D is in each case on each occurrence identically or differently selected from the group consisting of H, D, F, CH3and CD3and preferably represents H, and the other symbols and indices used have the above-mentioned meanings.

[0054] In a preferred embodiment, the group Q in the formula (1 ) or (1 a) represents a group of one of the following formulae (Q-1 ) to (Q-3); and the group Q in the formula (2) or (2a) represents a group of one of the following formulae (Q-4) to (Q-15) for p = 0 or a group of the formulae (Q-16) to (Q-19) for p = 1,

[0055]

[0056] The dotted bond here in each case denotes a linkage within the formula (1 ) or (2), and the * marks the position at which the group is coordinated to M, and X and R have the meanings given above. Preferably, not more than two groups X in each group Q which are not directly bonded to one another represent N, particularly preferably not more than one group X represents N. Very particularly preferably, all X represent CR and in particular CH, and all R in (Q-1 ) to (Q-3) and (Q-7) to (Q-9) represent H or D, in particular H.

[0057] For the compounds of the formula (2) or (2a), for p = 0, the groups (Q-4), (Q-5) and (Q-7) to (Q-9) are preferred, and for p = 1, the group (Q-16) is preferred.

[0058] In a preferred embodiment of the application, each of the two metals M in the compounds of the formula (1) or (2) or in the preferred embodiments is coordinated by exactly one carbon atom and one nitrogen atom, which are present in Q as coordinating atoms and as coordinating atoms D, in addition in each case by two partial ligands L. Thus, if the radical Q denotes a radical of the formula (Q-1), (Q-4), (Q-7), (Q-10) or (Q-13), i.e. is coordinated to each of the two metals M via a nitrogen atom, then the two radicals D preferably denote carbon atoms. If the radical Q denotes a radical of the formula (Q-2), (Q-5), (Q-8), (Q-11) or (Q-14), i.e. is coordinated to each of the two metals M via a carbon atom, then the two radicals D preferably denote nitrogen atoms. If the radical Q denotes a radical of the formula (Q-3), (Q-6), (Q-9), (Q-12) or (Q-15), i.e. is coordinated to the two metals M via one carbon atom and one nitrogen atom, then preferably the first of the two radicals D denotes a nitrogen atom and the other radical D denotes a carbon atom, so that each M is coordinated by one carbon atom and one nitrogen atom. The same applies analogously to the radicals of the formulae (Q-16) to (Q-19).

[0059] In a preferred embodiment of the application, the symbol X in the formula (1) or (2) or in the preferred embodiments represents CR, in particular CH, in each occurrence identically or differently, in addition.

[0060] In a further preferred embodiment of the application, p = 0 in the formula (2).

[0061] Preferred embodiments of the radical V, i.e. of the radical of the formula (3) or (4), are as follows.

[0062] Suitable embodiments of the radical of the formula (3) are the structures of the following formulae (6) to (9), and suitable embodiments of the radical of the formula (4) are the structures of the following formulae (10) to (14),

[0063]

[0064] where the symbols have the meanings given above.

[0065] The following applies to the preferred radicals R in the formulae (6) to (14):

[0066] R is, on each occurrence identically or differently, H, D, F, CN, OR 1 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, which can in each case be substituted by one or more radicals R 1substituted, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can in each case be substituted by one or more radicals R 1 substituted;

[0067] R 1 are on each occurrence, identically or differently, H, D, F, CN, OR 2 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, which can in each case be substituted by one or more radicals R 2 an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can in each case be substituted by one or more radicals R 2 two or more adjacent radicals R 1 may form a ring system with one another;

[0068] R 2 are on each occurrence, identically or differently, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms can be replaced by F.

[0069] The following applies to particularly preferred radicals R in formulae (6) to (14):

[0070] R are on each occurrence, identically or differently, H, D, F, CN, a straight-chain alkyl group having 1 to 4 C atoms or a branched or cyclic alkyl group having 3 to 6 C atoms, which can in each case be substituted by one or more radicals R 1 an aromatic or heteroaromatic ring system having 6 to 12 aromatic ring atoms, which can in each case be substituted by one or more radicals R 1 substituted;

[0071] R 1 are on each occurrence, identically or differently, H, D, F, CN, a straight-chain alkyl group having 1 to 4 C atoms or a branched or cyclic alkyl group having 3 to 6 C atoms, which can in each case be substituted by one or more radicals R 2 an aromatic or heteroaromatic ring system having 6 to 12 aromatic ring atoms, which can in each case be substituted by one or more radicals R 2 two or more adjacent radicals R 1 may form a ring system with one another;

[0072] R 2 are on each occurrence, identically or differently, H, D, F or an aliphatic or aromatic hydrocarbon radical having 1 to 12 C atoms.

[0073] In a preferred embodiment of the application, all groups X in the group of formula (3) 1 stand for CR, so that the central trivalent ring of formula (3) represents benzene. Particularly preferred, all groups X 1 stand for CH or CD, in particular for CH. In another preferred embodiment of the application, all groups X 1 stand for nitrogen atoms, so that the central trivalent ring of formula (3) represents triazine. Preferred embodiments of formula (3) are thus the structures of formula (6) and (7) mentioned above, in particular the structure of formula (6). The structure of formula (6) is particularly preferred the structure of formula (6') below,

[0074]

[0075] wherein the symbols have the meaning given above.

[0076] In another preferred embodiment of the application, all groups A in the group of formula (4) 2 stand for CR. Particularly preferred, all groups A 2 stand for CH. Preferred embodiments of formula (4) are thus the structures of formula (10) mentioned above. The structure of formula (10) is particularly preferred the structure of formula (10') or (10") below,

[0077]

[0078] wherein the symbols have the meaning given above and R preferably stands for H.

[0079] The group V is particularly preferred a group of formula (3) or a corresponding preferred embodiment.

[0080] The preferred groups A as present in the structures of formula (3) and (4) and (6) to (14) are described below. The group A can stand for an alkenyl group, an amide group, an ester group, an alkylene group, a methylidene ether group or a vicinal linked arylene or heteroarylene group of formula (5) identically or differently at each occurrence. If A stands for an alkenyl group, it is a cis-linked alkenyl group. If A stands for an alkylene group, it is preferably -CH2-CH2-. In case of an asymmetric group A, any orientation of the group is possible. This is exemplarily explained below with A = -C(=0)-0- as an example. This results in the following orientations of A, all of which are encompassed by the present application:

[0081]

[0082] In a preferred embodiment of the present application, A is, on each occurrence, identically or differently, preferably identically, selected from -C(=0)-0-, -C(=0)-NR'-, -CH2-CH2- or a group of the formula (5). The group A is particularly preferably, on each occurrence, identically or differently, preferably identically, selected from -C(=0)-0-, -C(=0)-NR'- or a group of the formula (5). The group of the formula (5) is very particularly preferred. Furthermore preferably, two groups A are identical and also identically substituted, and the third group A is different from the first two groups A, or all three groups A are identical and also identically substituted. Preferred combinations of the three groups A in the formulae (3) and (4) and preferred embodiments are:

[0083] A A A Formula (5) Formula (5) Formula (5) -C(=O)O- -C(=O)O- -C(=O)O- -C(=O)O- -C(=O)O- Formula (5) -C(=O)O- Formula (5) Formula (5) -C(=O)-NR'- -C(=O)-NR'- -C(=O)-NR'- -C(=O)-NR'- -C(=O)-NR'- Formula (5) -C(=O)-NR'- Formula (5) Formula (5) <![CDATA[-CH2-CH2-]]> <![CDATA[-CH2-CH2-]]> <![CDATA[-CH2-CH2-]]> <![CDATA[-CH2-CH2-]]> <![CDATA[-CH2-CH2-]]> Formula (5) <![CDATA[-CH2-CH2-]]> Formula (5) Formula (5)

[0084] If A represents -C(=0)-NR'-, then R' preferably represents, on each occurrence, identically or differently, a straight-chain alkyl group having 1 to 10 C atoms, or a branched or cyclic alkyl group having 3 to 10 C atoms, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which can in each case be substituted by one or more radicals R 1 , particularly preferably, on each occurrence, identically or differently, a straight-chain alkyl group having 1, 2, 3, 4 or 5 C atoms, or a branched or cyclic alkyl group having 3, 4, 5 or 6 C atoms, or an aromatic or heteroaromatic ring system having 6 to 12 aromatic ring atoms, which can in each case be substituted by one or more radicals R 1 , but is preferably unsubstituted.

[0085] Preferred embodiments of the group of the formula (5) are described below. The group of the formula (5) can represent a heteroaromatic five-membered ring or an aromatic or heteroaromatic six-membered ring. In a preferred embodiment of the present application, the group of the formula (5) contains a maximum of two heteroatoms, particularly preferably a maximum of one heteroatom, in the aromatic or heteroaromatic unit. This does not exclude that the substituents which can be bonded to this group can also contain heteroatoms. Furthermore, this definition does not exclude the ring closure of substituents which result in fused aromatic or heteroaromatic structures, for example naphthalene, benzimidazole, etc.

[0086] If two groups X 3 in the formula (5) represent carbon atoms, then preferred embodiments of the group of the formula (5) are the structures of the following formulae (15) to (31 ), and if one group X 3 represents a carbon atom and the other group X 3 in the same ring represents a nitrogen atom, then preferred embodiments of the group of the formula (5) are the structures of the following formulae (32) to (39),

[0087]

[0088] wherein the symbols have the meaning given above.

[0089] Particularly preferred are the six-membered aromatic and heteroaromatic groups of the above-mentioned formulae (15) to (19). Very particularly preferred is the ortho-phenylene radical, i.e. the radical of formula (15) shown above.

[0090] Here, adjacent substituents R can also form a ring system with one another, so that fused structures, i.e. fused aryl and heteroaryl radicals, such as naphthalene, quinoline, benzimidazole, carbazole, dibenzofuran or dibenzothiophene, can be formed. For the radical of formula (15) shown above, this type of ring formation is exemplarily shown below, which can lead to radicals of formulae (15a) to (15j), for example:

[0091]

[0092] wherein the symbols have the meaning given above.

[0093] In general, fused radicals can be fused at any position of the unit of formula (5), as is shown for the fused benzo radicals in formulae (15a) to (15c). Thus, the radicals fused to the unit of formula (5) in formulae (15d) to (15j) can also be fused at other positions of the unit of formula (5).

[0094] The radicals of formula (3) can preferably be represented by the following formulae (3a) to (3m) and the radicals of formula (4) can preferably be represented by the following formulae (4a) to (4m):

[0095]

[0096]

[0097] wherein the symbols have the meaning given above.X 2 preferably, identically or differently on each occurrence, CR.

[0098] In a preferred embodiment of the application, the radicals of formulae (3a) to (3m) are selected from the radicals of formulae (6a') to (6m') and the radicals of formulae (4a) to (4m) are selected from the radicals of formulae (10a') to (10m'),

[0099]

[0100]

[0101] wherein the symbols have the meaning given above.X 2 preferably, identically or differently on each occurrence, CR.

[0102] One particularly preferred embodiment of the group of formula (3) is a group of formula (6a") below,

[0103]

[0104] wherein the dotted bond has the definition given above.

[0105] The groups R in the formulae shown above are particularly preferably identically or differently H, D or an alkyl group having 1 to 4 C atoms. R is very particularly preferably = H. Thus very particularly preferred is the structure of formula (6a"') below,

[0106]

[0107] wherein the symbols have the meanings given above.

[0108] The bidentate monanionic partial ligands L are described below. The partial ligands can be identical or different. It is preferred here that the two partial ligands L coordinated to the same metal M are identical in each case and also identically substituted. This preferred manner is due to the simpler synthesis of the corresponding ligands.

[0109] In another preferred embodiment, all four bidentate partial ligands L for p = 0 or all six bidentate partial ligands L for p = 1 are identical and also identically substituted.

[0110] In another preferred embodiment of the application, the coordinating atoms of the bidentate partial ligands L are identically or differently selected from C, N, P, O, S and / or B in each occurrence, particularly preferably C, N and / or O and very particularly preferably C and / or N. Here the bidentate partial ligands preferably contain one carbon atom and one nitrogen atom or two carbon atoms or two nitrogen atoms or two oxygen atoms or one oxygen atom and one nitrogen atom as coordinating atoms. Here, the coordinating atoms of each partial ligand L can be identical or they can be different. Preferably, at least one of the two bidentate partial ligands L coordinated to the same metal M contains one carbon atom and one nitrogen atom or two carbon atoms as coordinating atoms, particularly one carbon atom and one nitrogen atom. Particularly preferably, all bidentate partial ligands contain one carbon atom and one nitrogen atom or two carbon atoms as coordinating atoms, particularly one carbon atom and one nitrogen atom. Thus, this is particularly preferably a metal complex in which all partial ligands are ortho-metalated, i.e. form a metacycle with the metal M which contains at least one metal-carbon bond.

[0111] It is furthermore preferred that the metacycle formed by the metal M and the bidentate partial ligands L is a five-membered ring, which is particularly preferred if the coordinating atoms are C and N, N and N or N and O. If the coordinating atoms are O, a six-membered metacycle can also be preferred. This is depicted below by way of example:

[0112]

[0113] wherein N denotes a coordinating nitrogen atom, C denotes a coordinating carbon atom and O denotes a coordinating oxygen atom, and the drawn carbon atom denotes an atom of the bidentate partial ligand L.

[0114] In a preferred embodiment of the application, at least one and particularly preferably all bidentate partial ligands L of each metal M are, identically or differently on each occurrence, selected from the structures of the following formulae (L-1), (L-2) or (L-3),

[0115]

[0116] wherein the dotted bond denotes a bond from the partial ligand L to V, i.e. to the group of formula (3) or (4) or preferred embodiment, and the following applies to the other symbols used:

[0117] CyCis, on each occurrence identically or differently, a substituted or unsubstituted aryl or heteroaryl group having 5 to 14 aromatic ring atoms which coordinates to M via a carbon atom and which is bonded to CyDvia a covalent bond;

[0118] CyDis, on each occurrence identically or differently, a substituted or unsubstituted heteroaryl group having 5 to 14 aromatic ring atoms which coordinates to M via a nitrogen atom or via a carbene carbon atom and which is bonded to CyCvia a covalent bond;

[0119] Here a plurality of optional substituents can form a ring system with one another; furthermore, the optional groups are preferably selected from the above-mentioned groups R.

[0120] Here CyDin the partial ligands of formulae (L-1) and (L-2) is preferably coordinated via a neutral nitrogen atom or via a carbene carbon atom, in particular via a neutral nitrogen atom. Furthermore, one of the two groups CyDin the ligand of formula (L-3) is preferably coordinated via a neutral nitrogen atom and the other of the two groups CyDis coordinated via an anionic nitrogen atom. Furthermore, CyCin the partial ligands of formulae (L-1) and (L-2) is preferably coordinated via an anionic carbon atom.

[0121] If a plurality of substituents, in particular a plurality of groups R, form a ring system with one another, this can be formed from substituents which are bonded to directly adjacent carbon atoms. Furthermore, the substituents on CyCand CyDin formulae (L-1) and (L-2) or the substituents on the two groups CyDin formula (L-3) can also be annulated with one another, such that CyCand CyDor the two groups CyDcan also form a single fused aryl or heteroaryl group as bidentate ligand.

[0122] In a preferred embodiment of the application, CyC is an aryl or heteroaryl group having 6 to 13 aromatic ring atoms, particularly preferably having 6 to 10 aromatic ring atoms, very particularly preferably having 6 aromatic ring atoms, which is coordinated to the metal via a carbon atom, can be substituted by one or more radicals R and is bonded to CyD via a covalent bond.

[0123] Preferred embodiments of the group CyC are the structures of the following formulae (CyC-1 ) to (CyC-20),

[0124]

[0125] wherein CyC is bonded to CyD in each case in the position indicated by # and is coordinated to the metal in the position indicated by *, R has the definition given above and the following applies to the other symbols used:

[0126] X is on each occurrence, identically or differently, CR or N, with the proviso that a maximum of two symbols X in each ring represent N;

[0127] W is NR, O or S;

[0128] with the proviso that, if the moiety Ligand L is bonded to V, i.e. to a group of the formula (3) or (4), via CyC, one symbol X represents C and the group V, i.e. a group of the formula (3) or (4) or a preferred embodiment, is bonded to this carbon atom. If the moiety Ligand L is bonded to a group of the formula (3) or (4) via the group CyC, the bonding preferably takes place via the position marked by “o” in the above formulae, so that the symbol X marked by “o” preferably represents C. The above structures not containing a symbol X marked by “o” are preferably not bonded to a group of the formula (3) or (4), since the bonding of these groups to the group V is unfavourable for steric reasons.

[0129] Preferably, a maximum of two symbols X in total in CyC represent N, particularly preferably a maximum of one symbol X in CyC represents N, very particularly preferably all symbols X represent CR, with the proviso that, if CyC is bonded directly to the group V, i.e. to a group of the formula (3) or (4), one symbol X represents C and the bridging group of the formula (3) or (4) or a preferred embodiment is bonded to this carbon atom.

[0130] Particularly preferred groups CyC are the groups of the following formulae (CyC-1 a) to (CyC-20a),

[0131]

[0132]

[0133] wherein the symbols have the meanings given above and if CyCis directly bonded to a group V, i.e. to a group of formula (3) or (4), then the group R is not present and the group of formula (3) or (4) or of the preferred embodiments is bonded to the respective carbon atom. If the group CyCis directly bonded to a group of formula (3) or (4), the bonding preferably takes place via the position marked by "o" in the above formulae, so that the group R is preferably not present at this position. The above structures not containing the carbon atom marked by "o" are preferably not directly bonded to a group of formula (3) or (4).

[0134] Preferred groups of the groups (CyC-1 ) to (CyC-20) are the groups (CyC-1 ), (CyC-3), (CyC-8), (CyC-10), (CyC-12), (CyC-13) and (CyC-16), and particularly preferred are the groups (CyC-1 a), (CyC-3a), (CyC-8a), (CyC-10a), (CyC-12a), (CyC-13a) and (CyC-16a).

[0135] In another preferred embodiment of the application, CyD is a heteroaryl group having 5 to 13 aromatic ring atoms, particularly preferably having 6 to 10 aromatic ring atoms, which can be coordinated to a metal via a neutral nitrogen atom or via a carbene carbon atom and which can be substituted by one or more groups R and which is bonded to CyC via a covalent bond.

[0136] Preferred embodiments of the group CyD are the structures of the following formulae (CyD-1 ) to (CyD-14),

[0137]

[0138] wherein the group CyD is in each case bonded to CyC at the position indicated by # and coordinated to the metal at the position indicated by * and wherein X, W and R have the meanings given above, with the proviso that if CyD is directly bonded to a group V, i.e. to a group of formula (3) or (4), then one symbol X stands for C and the bridging group of formula (3) or (4) or of the preferred embodiments is bonded to this carbon atom. If the group CyD is directly bonded to a group of formula (3) or (4), the bonding preferably takes place via the position marked by "o" in the above formulae, so that the symbol X marked by "o" preferably stands for C. The above structures not containing the symbol X marked by "o" are preferably not directly bonded to a group of formula (3) or (4) since the bonding of these groups to a group V is unfavourable for steric reasons.

[0139] The radicals (CyD-1) to (CyD-4), (CyD-7) to (CyD-10), (CyD-13) and (CyD-14) are coordinated to the metal via a neutral nitrogen atom, (CyD-5) and (CyD-6) are coordinated to the metal via a carbene carbon atom and (CyD-11) and (CyD-12) are coordinated to the metal via an anionic nitrogen atom.

[0140] Preferably, at most two of the total number of symbols X in CyD represent N, particularly preferably at most one of the symbols X in CyD represents N, and especially preferably all symbols X represent CR, with the proviso that, if CyD is directly bonded to a radical V, i.e. to a radical of the formula (3) or (4), one symbol X represents C and the bridging radical of the formula (3) or (4) or of the preferred embodiment is bonded to this carbon atom.

[0141] Particularly preferred radicals CyD are radicals of the following formulae (CyD-1a) to (CyD-14b),

[0142]

[0143] where the symbols used have the meanings given above and, if CyD is directly bonded to a radical V, i.e. to a radical of the formula (3) or (4), the radical R is not present and the bridging radical of the formula (3) or (4) or of the preferred embodiment is bonded to the respective carbon atom. If CyD is directly bonded to a radical of the formula (3) or (4), the bonding preferably takes place via the position marked by "o" in the formulae mentioned above, so that the radical R is preferably not present at this position. The structures mentioned above which do not contain a carbon atom marked by "o" are preferably not directly bonded to a radical of the formula (3) or (4).

[0144] The preferred radicals of the radicals (CyD-1) to (CyD-14) are the radicals (CyD-1), (CyD-2), (CyD-3), (CyD-4), (CyD-5) and (CyD-6), in particular (CyD-1), (CyD-2) and (CyD-3), and particularly preferred are the radicals (CyD-1a), (CyD-2a), (CyD-3a), (CyD-4a), (CyD-5a) and (CyD-6a), in particular (CyD-1a), (CyD-2a) and (CyD-3a).

[0145] In a preferred embodiment of the application, CyC is an aryl or heteroaryl group having 6 to 13 aromatic ring atoms, and at the same time CyD is a heteroaryl group having 5 to 13 aromatic ring atoms. CyC is particularly preferably an aryl or heteroaryl group having 6 to 10 aromatic ring atoms, and at the same time CyD is a heteroaryl group having 5 to 10 aromatic ring atoms. CyC is very particularly preferably an aryl or heteroaryl group having 6 aromatic ring atoms, in particular phenyl, and CyD is a heteroaryl group having 6 to 10 aromatic ring atoms. Here CyC and CyD can be substituted by one or more radicals R.

[0146] The above-mentioned preferred groups (CyC-1) to (CyC-20) and (CyD-1) to (CyD-14) can be combined with one another in the partial ligands of the formulae (L-1) and (L-2) as desired, provided that at least one of the groups CyC and CyD has a suitable point of attachment to the group of the formula (3) or (4), wherein the suitable point of attachment in the above formulae is indicated by "o". It is particularly preferred that the groups CyC and CyD mentioned above as being particularly preferred, i.e. the groups of the formulae (CyC-1a) to (CyC-20a) and (CyD-1a) to (CyD-14b), are combined with one another, provided that at least one of the preferred groups CyC or CyD has a suitable point of attachment to the group of the formula (3) or (4), wherein the suitable point of attachment in the above formulae is indicated by "o". Combinations in which neither CyC nor CyD has such a suitable point of attachment to the bridging group of the formula (3) or (4) are therefore not preferred.

[0147] It is very particularly preferred that one of the groups (CyC-1), (CyC-3), (CyC-8), (CyC-10), (CyC-12), (CyC-13) and (CyC-16), in particular one of the groups (CyC-1a), (CyC-3a), (CyC-8a), (CyC-10a), (CyC-12a), (CyC-13a) and (CyC-16a), is combined with one of the groups (CyD-1), (CyD-2) and (CyD-3), and in particular with one of the groups (CyD-1a), (CyD-2a) and (CyD-3a).

[0148] Preferred partial ligands (L-1) are the structures of the following formulae (L-1-1) and (L-1-2), and preferred partial ligands (L-2) are the structures of the following formulae (L-2-1) to (L-2-3),

[0149]

[0150] wherein the symbols used have the meanings given above, * indicates a coordination site to the metal M and "o" denotes a bond position to a group V, i.e. to a group of formula (3) or (4).

[0151] Particularly preferred partial ligands (L-1) are structures of the following formulae (L-1-1a) and (L-1-2b) and particularly preferred partial ligands (L-2) are structures of the following formulae (L-2-1a) to (L-2-3a),

[0152]

[0153] wherein the symbols used have the meanings given above and "o" denotes a bond position to a group V, i.e. to a group of formula (3) or (4).

[0154] The above-mentioned preferred groups CyD in the partial ligands of formula (L-3) can likewise be combined with one another as desired, wherein neutral groups CyD, i.e. groups (CyD-1) to (CyD-10), (CyD-13) or (CyD-14), are combined with anionic groups CyD, i.e. groups (CyD-11) or (CyD-12), provided that at least one of the preferred groups CyD has a suitable connection site to a group of formula (3) or (4), wherein the suitable connection site in the above formulae is indicated by "o".

[0155] If two groups R (one of the groups mentioned in formulae (L-1) and (L-2) is bound to CyC and the other to CyD or one of the groups mentioned in formula (L-3) is bound to one group CyD and the other to the other group CyD) form a ring system with one another, bridged partial ligands and also partial ligands which overall represent a single larger heteroaryl group, for example benzo[h]quinoline and the like, can be produced. The cyclisation between the substituents on CyC and CyD in formulae (L-1) and (L-2) or between the substituents on the two groups CyD in formula (L-3) is preferably carried out via one of the following groups of formulae (40) to (49),

[0156]

[0157] wherein R 1 have the meanings given above and the dashed bond indicates a bond to CyC or CyD. The asymmetric groups of the above-mentioned ones can be incorporated in each of the two orientations, for example in the case of the group of formula (49) the oxygen atom can be bound to the group CyC and the carbonyl group can be bound to the group CyD or the oxygen atom can be bound to the group CyD and the carbonyl group can be bound to the group CyC.

[0158] If the ring formation thus results in a six-membered ring, groups of the formula (46) are particularly preferred, which six-membered ring is illustrated, for example, below by the formulae (L-22) and (L-23).

[0159] Preferred ligands which are formed by ring formation of two groups R on different rings are the structures of the formulae (L-4) to (L-31) shown below,

[0160]

[0161]

[0162] where the symbols used have the meanings given above and "o" indicates the position at which the moiety of the ligand is attached to the group of the formula (3) or (4).

[0163] In one preferred embodiment of the moiety of the formula (L-4) to (L-31), one symbol X stands for N and the other symbols X stand for CR, or all symbols X stand for CR.

[0164] In another embodiment of the application, in the case where one of the atoms X stands for N in the groups (CyC-1) to (CyC-20) or (CyD-1) to (CyD-14) or in the moieties of the ligand (L-1-1) to (L-2-3), (L-4) to (L-31), it is preferred that a group R which is different from hydrogen or deuterium is bound as substituent adjacent to this nitrogen atom. This applies analogously to the preferred structures (CyC-1a) to (CyC-20a) or (CyD-1a) to (CyD-14b), in which a group R which is different from hydrogen or deuterium is preferably bound as substituent adjacent to the non-coordinating nitrogen atom. This substituent R is preferably selected from the group of the following radicals: CF3, OR 1 (wherem R 1 represents an alkyl radical having 1 to 10 C atoms), an alkyl radical having 1 to 10 C atoms, in particular a branched or cyclic alkyl radical having 3 to 10 C atoms, a dialkylamino radical having 2 to 10 C atoms, an aromatic or heteroaromatic ring system or an aralkyl or heteroaralkyl radical. These radicals are sterically bulky radicals. Furthermore preferably, the group R can also form a ring with the adjacent group R.

[0165] Another suitable bidentate moiety of the ligand is a moiety of the formula (L-32) or (L-33) below,

[0166]

[0167] where R has the meaning given above, * indicates the coordination site to the metal, "o" indicates the position of attachment of the moiety of the ligand to the group of the formula (3) or (4) and the following applies to the other symbols used:

[0168] X is on each occurrence, identically or differently, CR or N, with the proviso that in each ring at most one symbol X stands for N and furthermore with the proviso that one symbol X stands for C, and the partial ligand is bonded to the group V, i.e. to the group of the formula (3) or (4), via this carbon atom.

[0169] If the two groups R bonded to adjacent carbon atoms in the partial ligands (L-32) and (L-33) form an aromatic ring with each other, it is preferably a structure of the following formula (50) together with the two adjacent carbon atoms,

[0170]

[0171] where the dotted bond indicates the attachment of the group in the partial ligand, and Y stands on each occurrence, identically or differently, for CR 1 or N, and preferably at most one symbol Y stands for N. In one preferred embodiment of the partial ligands (L-32) or (L-33), there is at most one group of the formula (50). In one preferred embodiment of the application, in the partial ligands of the formula (L-32) and (L-33), in total 0, 1 or 2 symbols X and Y, if present, stand for N. Particularly preferably, in total 0 or 1 symbols X and Y, if present, stand for N.

[0172] Furthermore, suitable bidentate partial ligands are structures of the following formulae (L-34) to (L-38), wherein preferably at most one of the two bidentate partial ligands L per metal represents one of these structures,

[0173]

[0174] where the partial ligands (L-34) to (L-36) are each coordinated to the metal via the explicitly drawn nitrogen atom and the negatively charged oxygen atom, and the partial ligands (L-37) and (L-38) are coordinated to the metal via the two oxygen atoms, X stands on each occurrence, identically or differently, for CR or N, and at most two groups X per ring stand for N, and “o” indicates the position at which the partial ligand L is attached to the group of the formula (3) or (4).

[0175] The preferred embodiments of X described above are also preferred for the partial ligands of the formulae (L-34) to (L-36).

[0176] Preferred partial ligands of the formulae (L-34) to (L-36) are thus the partial ligands of the following formulae (L-34a) to (L-36a),

[0177]

[0178] wherein the symbols used have the meanings given above and "o" indicates the position at which the partial ligand L is attached to the group of formula (3) or (4).

[0179] In these formulae, R particularly preferably represents hydrogen, wherein "o" indicates the position at which the partial ligand L is attached to the group V, i.e. to the group of formula (3) or (4) or of the preferred embodiments, and the structures are thus those of formulae (L-34b) to (L-36b),

[0180]

[0181] wherein the symbols used have the meanings given above.

[0182] Preferred substituents which can be present on the partial ligands described above and on A, if A represents a group of formula (5), are described below.

[0183] In a preferred embodiment of the application, the compound according to the application contains two substituents R which are bonded to adjacent carbon atoms and which form an aliphatic ring with one another of one of the following formulae. The two substituents R which form the aliphatic ring can be present on the bridging group of formula (3) or (4) or of the preferred embodiments and / or on one or more of the bidentate partial ligands L. The aliphatic ring formed by the two substituents R in a ring with one another is preferably described by one of the following formulae (51) to (57),

[0184]

[0185] wherein R 1 and R 2 have the definitions given above, the dashed bond indicates the attachment of two carbon atoms in the ligand, and furthermore:

[0186] Z 1 , Z 3 is on each occurrence, identically or differently, C(R 3 )2, O, S, NR 3 or C(=O);

[0187] Z 2 is C(R 1 )2, O, S, NR 3 or C(=O);

[0188] G is an alkylidene radical having 1, 2 or 3 C atoms, which can be substituted by one or more radicals R 2 , or is -CR 2 =CR 2 - or an ortho- linked arylidene or heteroaryliden radical having 5 to 14 aromatic ring atoms, which can be substituted by one or more radicals R 2 ;

[0189] R 3 in each occurrence are identically or differently H, F, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms, where the alkyl or alkoxy groups can in each case be substituted by one or more radicals R 2 , where one or more non-adjacent CH2 groups can be replaced by R 2 , C≡C, Si(R 2 )2, C=0, NR 2 , O, S or CONR 2 , or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can in each case be substituted by one or more radicals R 2 , or an aryloxy or heteroaryloxy group having 5 to 24 aromatic ring atoms, which can be substituted by one or more radicals R 2 ; here two radicals R 2 bonded to the same carbon atom can form an aliphatic or aromatic ring system with one another and thus a spiro system; furthermore, R 3 may form an aliphatic ring system with an adjacent radical R 3 or R 1 ;

[0190] with the proviso that in these groups no two heteroatoms are directly bonded to one another and no two groups C=0 are directly bonded to one another.

[0191] In a preferred embodiment of the application, R 3 is not equal to H.

[0192] In the structures of the above-mentioned formulae (51 ) to (57) and in the other embodiments of these structures indicated as preferred, a double bond is formally formed between two carbon atoms. This means that if these two carbon atoms are bonded into an aromatic or heteroaromatic system and the bond between these two carbon atoms is thus formally between the bond order of a single bond and the bond order of a double bond, a simplification of the chemical structure. The depiction of the formal double bond is thus not to be interpreted as a restriction of the structure, but it is obvious to the person skilled in the art that this is an aromatic bond.

[0193] If adjacent groups in a structure according to the application form an aliphatic ring system, it is preferred that it does not contain an acidic benzylic proton. A benzylic proton means a proton which is bonded to a carbon atom which is directly bonded to a ligand. This can be achieved by the carbon atom of the aliphatic ring system which is directly bonded to the aryl or heteroaryl group being completely substituted and not containing a bonded hydrogen atom. Thus, the absence of an acidic benzylic proton in formulae (51 ) to (53) is achieved by Z 1 and Z 3 , if they represent C(R3 )2, then R 3 is defined in such a way that it is not hydrogen. This can also be achieved in that the carbon atom of the aliphatic ring system which is directly bound to the aryl or heteroaryl group is a bridgehead of a bicyclic or polycyclic structure. Due to the spatial structure of the bicyclic or polycyclic structure, the acidity of the proton bound to the bridgehead carbon atom is significantly smaller than that of a benzylic proton on a carbon atom which is not bound to a carbon atom in a bicyclic or polycyclic structure, and said proton bound to the bridgehead carbon atom is regarded as a non-acidic proton in the sense of the present application. Thus, the absence of an acidic benzylic proton is achieved in formulae (54) to (57) by the fact that it is a bicyclic structure, which means that if R 1 represents H, then R 1 is significantly less acidic than a benzylic proton, because the corresponding anion of the bicyclic structure is not resonance-stabilized. Even if R 1 represents H in formulae (54) to (57), this is therefore a non-acidic proton in the sense of the present application.

[0194] In one preferred embodiment of the structures of formulae (51) to (57), the group Z 1 , Z 2 and Z 3 represent at most one heteroatom, in particular O or NR 3 , and the other groups represent C(R 3 )2or C(R 1 )2, or Z 1 and Z 3 represent, identically or differently on each occurrence, O or NR 3 and Z 2 represents C(R 1 )2. In one particularly preferred embodiment of the present application, Z 1 and Z 3 represent, identically or differently on each occurrence, C(R 3 )2and Z 2 represents C(R 1 )2and particularly preferably C(R 3 )2or CH2.

[0195] Preferred embodiments of formula (51) are thus the structures of formulae (51-A), (51-B), (51-C) and (51-D), and one particularly preferred embodiment of formula (51-A) is the structure of formulae (51-E) and (51-F),

[0196]

[0197] wherein R 1 and R 3 have the meanings given above, and Z 1 , Z2 and Z 3 identically or differently at each occurrence, represent O or NR 3 .

[0198] Preferred embodiments of formula (52) are the structures of formulae (52-A) to (52-F),

[0199]

[0200] wherein R 1 and R 3 have the meanings given above and Z 1 , Z 2 and Z 3 identically or differently at each occurrence, represent O or NR 3 .

[0201] Preferred embodiments of formula (53) are the structures of formulae (53-A) to (53-E),

[0202]

[0203] wherein R 1 and R 3 have the meanings given above and Z 1 , Z 2 and Z 3 identically or differently at each occurrence, represent O or NR 3 .

[0204] In one preferred embodiment of the structures of formula (54), the group R 1 bonded to the bridgehead represents H, D, F or CH3. Furthermore preferably, Z 2 represents C(R 1 )2or O, and particularly preferably C(R 3 )2. Preferred embodiments of formula (54) are thus the structures of formulae (54-A) and (54-B), and one particularly preferred embodiment of (54-A) is the structure of formula (54-C),

[0205]

[0206] wherein the symbols used have the meanings given above.

[0207] In one preferred embodiment of the structures of formulae (55), (56) and (57), the group R 1 bonded to the bridgehead represents H, D, F or CH3. Furthermore preferably, Z 2 represents C(R 1)2. Preferred embodiments of formulae (55), (56) and (57) are thus the structures of formulae (55-A), (56-A) and (57-A),

[0208]

[0209] wherein the symbols used have the meanings given above.

[0210] Furthermore, preferably, the group G in formulae (54), (54-A), (54-B), (54-C), (55), (55-A), (56), (56-A), (57) and (57-A) represents a 1,2- ethylene group, which can be substituted by one or more groups R 2 , wherein R 2 preferably represents, on each occurrence identically or differently, H or an alkyl group having 1 to 4 C atoms, or an ortho-arylene group having 6 to 10 C atoms, which can be substituted by one or more groups R 2 , but is preferably unsubstituted, in particular an ortho-phenylene group, which can be substituted by one or more groups R 2 , but is preferably unsubstituted.

[0211] In another preferred embodiment of the application, R 3 on each occurrence identically or differently, F, a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherein in each case one or more non-adjacent CH2 groups can be replaced by R 2 C=CR 2 and one or more H atoms can be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 14 aromatic ring atoms, which may 2 be substituted by one or more groups R 3 ; here two groups R 3 bonded to the same carbon atom can form an aliphatic or aromatic ring system with one another and thus a spiro system; furthermore, R 1 may form an aliphatic ring system with an adjacent group R or R .

[0212] In a particularly preferred embodiment of the application, R 3 on each occurrence identically or differently, F, a straight-chain alkyl group having 1 to 3 C atoms, in particular methyl, or an aromatic or heteroaromatic ring system having 5 to 12 aromatic ring atoms, which may 2are preferably not substituted; here two radicals R 3 may form an aliphatic or aromatic ring system with one another and thus form a spiro ring system; furthermore, R 3 may form an aliphatic ring system with adjacent radicals R or R 1 .

[0213] Examples of particularly suitable groups of the formula (51 ) are the groups shown below:

[0214]

[0215]

[0216] Examples of particularly suitable groups of the formula (52) are the groups shown below:

[0217]

[0218] Examples of particularly suitable groups of the formula (53), (56) and (57) are the groups shown below:

[0219]

[0220] Examples of particularly suitable groups of the formula (54) are the groups shown below:

[0221]

[0222] Examples of particularly suitable groups of the formula (55) are the groups shown below:

[0223]

[0224] If the groups R are bound in a bidentate partial ligand L or in a ligand or in the divalent arylene or heteroarylene group of the formula (5) bound in the formula (3) or (4) or in the preferred embodiments, these groups R are preferably, on each occurrence identically or differently, selected from 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 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, where the alkyl or alkenyl groups can in each case be substituted by one or more radicals R 1 or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which can in each case be substituted by one or more radicals R 1 ; here two adjacent radicals R or R 1It is also possible for these groups R to form, together with one another, an aliphatic or aromatic ring system which is mono- or polycyclic. These groups R are particularly preferably, on each occurrence identically or differently, H, D, F, N(R 1 )2, a straight-chain alkyl group having 1 to 6 C atoms or branched or cyclic alkyl group having 3 to 10 C atoms, wherein one or more H atoms can be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, preferably having 6 to 13 aromatic ring atoms, which can in each case be substituted by one or more radicals R 1 ; here two adjacent radicals R or R 1 may also form, together with one another, an aliphatic or aromatic ring system which is mono- or polycyclic.

[0225] The preferred radicals R 1 are, on each occurrence identically or differently, H, D, F, N(R 2 )2, CN, a straight-chain alkyl group having 1 to 10 C atoms or alkenyl group having 2 to 10 C atoms or branched or cyclic alkyl group having 3 to 10 C atoms, wherein the alkyl groups can in each case be substituted by one or more radicals R 2 , or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which can in each case be substituted by one or more radicals R 2 ; here two or more adjacent R 1 may also form, together with one another, an aliphatic ring system which is mono- or polycyclic. Particularly preferred radicals R 1 bonded to R are, on each occurrence identically or differently, H, F, CN, a straight-chain alkyl group having 1 to 5 C atoms or branched or cyclic alkyl group having 3 to 5 C atoms, which can in each case be substituted by one or more radicals R 2 , or an aromatic or heteroaromatic ring system having 5 to 13 aromatic ring atoms, which can in each case be substituted by one or more radicals R 2 ; here two or more adjacent R 1 may also form, together with one another, an aliphatic ring system which is mono- or polycyclic.

[0226] The preferred radicals R 2 are, on each occurrence identically or differently, H, F, or an aliphatic hydrocarbon group having 1 to 5 C atoms or an aromatic hydrocarbon group having 6 to 12 C atoms; here two or more substituents R 2 may also form, together with one another, an aliphatic ring system which is mono- or polycyclic.

[0227] The above-mentioned preferred embodiments can be combined with one another as desired within the scope of the claims. In one particularly preferred embodiment of the application, the above-mentioned preferred embodiments apply simultaneously.

[0228] The compounds according to the application are chiral structures. Depending on the precise structure of the complex and the ligand, the formation of diastereomers and pairs of enantiomers is possible. Thus, the complexes according to the application include mixtures of various diastereomers or the corresponding racemates as well as the individually isolated diastereomers or enantiomers.

[0229] In the ortho-metalation reaction of the ligand, the accompanying bimetallic complex is usually formed as a mixture of ΛΛ and ΔΔ isomers as well as ΔΛ and ΛΔ isomers. The same applies to the trimetallic complex. ΛΛ and ΔΔ isomers form a pair of enantiomers, as do ΔΛ and ΛΔ isomers. The diastereomeric pairs can be separated using conventional methods, for example chromatography or fractional crystallization. Depending on the symmetry of the ligand, stereocenters can be present simultaneously, meaning that meso forms are also possible. Thus, for example in C 2v or C s In the case of ortho-metalation of symmetrical ligands, ΛΛ and ΔΔ isomers (racemate, C2 symmetry) and ΛΔ isomers (meso compound, C s The preparation and separation of diastereomeric pairs is intended to be explained with reference to the following examples.

[0230]

[0231] The racemic separation of ΔΔ and ΛΛ isomers can be carried out by fractional crystallization of diastereomeric salt pairs or by conventional methods on chiral columns. For this purpose, the neutral Ir(III) complex can be oxidized (for example using peroxides, H2O2 or electrochemical oxidation), a salt of an enantiomerically pure monanionic base (chiral base) can be added to the cationic Ir(III) / Ir(IV) or dicationic Ir(IV) / Ir(IV) complex produced in this way, the diastereomeric salts produced in this way can be separated by fractional crystallization, and these can then be reduced to enantiomerically pure neutral complexes by means of a reducing agent (for example zinc, hydrazine hydrate, ascorbic acid, etc.), as schematically shown below.

[0232]

[0233] The enantiomerically pure complexes can also be synthesized specifically as depicted in the following scheme. For this purpose, the diastereomeric pairs formed in the ortho-metalation, as described above, are separated, brominated and then reacted by cross-coupling reaction with a boronic acid R*A-B(OH)2containing a chiral group R* (preferably > 99% enantiomeric excess). The diastereomeric pairs formed can be separated by silica gel chromatography or by fractional crystallization using conventional methods. Enantiomerically enriched or enantiomerically pure complexes are thus obtained. The chiral group can then optionally be cleaved off or can also remain in the molecule.

[0234]

[0235]

[0236] The complexes are usually formed in the ortho-metallation as a mixture of diastereomeric pairs. However, it is also possible to synthesize only one of the diastereomeric pairs in particular, because depending on the ligand structure, the other one does not form or does not form preferentially for steric reasons. This is intended to be illustrated with the following examples.

[0237]

[0238] Due to the high steric demand of the tert-butyl groups, the racemates of ΛΛ and ΔΔ isomers form preferentially or only in the ortho-metallation. In the meso form (C s In the symmetrical) meso isomer, the bonds of the 2-phenylpyridine ligand highlighted by circles protrude out of the drawing plane. Due to the high steric demand of the tert-butyl groups on the pyridine ring, the meso isomer does not form or does not form preferentially. In contrast, in the racemate (C2 symmetry), one of the bonds to the 2-phenylpyridine ligand points into the drawing plane and the other one out of the drawing plane. Depending on the steric demand of the groups, the racemate is preferably formed or only formed.

[0239] The complexes according to the application can be prepared, inter alia, by the following routes. For this purpose, 12- or 18-dentate ligands are prepared and then coordinated to the metal M by an ortho-metallation reaction. For this purpose, the iridium or rhodium salt is usually reacted with the corresponding free ligand.

[0240] The application therefore also relates to a process for the preparation of a compound according to the application by reacting the corresponding free ligand with a metal alkoxide of the formula (58), with a metal diketonate of the formula (59), with a metal halide of the formula (60) or with a metal carboxylate of the formula (61),

[0241]

[0242] in which M and R have the meanings indicated above, Hal = F, CI, Br or I, and the iridium or rhodium starting materials can also be in the form of the corresponding hydrates. Here, R preferably represents an alkyl radical having 1 to 4 C atoms.

[0243] Equally usable are iridium or rhodium compounds which carry alcohol anions and / or halogen anions and / or hydroxyl groups as well as diketonate anion groups. These compounds can also be charged. Corresponding iridium compounds which are particularly suitable as starting materials are disclosed in WO 2004 / 085449. Particularly suitable is [IrCI2(acac)2] ─metal complexes with acetylacetonate derivatives as ligands, such as Ir(acac)3or tris(2,2,6,6-tetramethylheptane-3,5-dionato)iridium, and IrCl3x H2O, wherein x usually represents a number from 2 to 4.

[0244] The synthesis of the complexes is preferably carried out as described in WO 2002 / 060910 and WO 2004 / 085449. The synthesis can also be activated here, for example, by heating, photochemically and / or by means of microwave irradiation. Furthermore, the synthesis can also be carried out in an autoclave at high pressure and / or at high temperature.

[0245] The reaction can be carried out without the addition of solvents or melting aids in the melt of the corresponding ligand to be orthometallated. If necessary, solvents or melting aids can also be added. Suitable solvents are protic or aprotic solvents, such as aliphatic and / or aromatic alcohols (methanol, ethanol, isopropanol, tert-butanol and the like), oligomeric and polymeric alcohols (ethylene glycol, 1,2-propanediol, glycerol and the like), alcohol ethers (ethoxyethanol, diethylene glycol, triethylene glycol, polyethylene glycol and the like), ethers (diethylene glycol dimethyl ether and triethylene glycol dimethyl ether, diphenyl ether and the like), aromatic, heteroaromatic and / or aliphatic hydrocarbons (toluene, xylene, mesitylene, chlorobenzene, pyridine, lutidine, quinoline, isoquinoline, tridecane, hexadecane and the like), amides (DMF, DMAC and the like), lactams (NMP), sulfoxides (DMSO) or sulfones (dimethyl sulfone, sulfolane and the like). Suitable melting aids are compounds which are in solid form at room temperature, but melt and dissolve the reactants to form a homogeneous melt when the reaction mixture is heated. Particular preference is given to diphenyl, m-terphenyl, triphenylene, R- or S-binol or the corresponding racemates, 1,2- or 1,3- or 1,4-bisphenyloxybenzene, triphenylphosphine oxide, 18-crown-6, phenol, 1-naphthol, hydroquinone and the like. Particular preference is given to the use of hydroquinone.

[0246] These processes, optionally followed by purification, for example recrystallization or sublimation, make it possible to obtain the compounds of the formula (1) according to the application in high purity, preferably greater than 99% (determined by means of 1 H-NMR and / or HPLC).

[0247] The compounds according to the invention can also become soluble through suitable substitution, for example by relatively long-chain alkyl groups (about 4 to 20 C atoms), particularly branched alkyl groups, or optionally substituted aryl groups, such as xylyl, mesitylene, or branched terphenyl or tetraphenyl groups. In particular, the use of fused aliphatic groups, for example, those shown by formulas (51) to (57) disclosed above, results in a significant improvement in the solubility of the metal complex. Thus, compounds of this type are soluble in common organic solvents such as toluene or xylene at room temperature at concentrations sufficient to handle the complexes from solution. These soluble compounds are particularly suitable for handling from solution, for example, by printing methods.

[0248] Processing the metal complexes according to the invention from the liquid phase, for example by spin coating or printing, requires formulations of the metal complexes according to the invention. These formulations can be, for example, solutions, dispersions, or emulsions. For this purpose, mixtures of two or more solvents are preferred. Suitable and preferred solvents include, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, naphthalene, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, dimethylbenzene, etc. Alkane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fonone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indene, NMP, p-methylisopropylbenzene, styrene Ethers, 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, pentaphenyl, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, hexamethylindene, 2-methylbiphenyl, 3-methylbiphenyl, 1-methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, diethyl sebacate, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexyl hexanoate, or mixtures of these solvents.

[0249] Therefore, the present invention also relates to a formulation comprising at least one compound according to the invention and at least one additional compound. The additional compound may be, for example, a solvent, particularly one of the aforementioned solvents or a mixture of these solvents. However, the additional compound may also be another organic or inorganic compound, which is also used in electronic devices, such as matrix materials. This additional compound may also be polymerized.

[0250] The metal complexes according to the application or the preferred embodiments detailed above can be used in electronic devices as active components or as oxygen sensors. The present application therefore also relates to the use of a compound according to the application in an electronic device or as an oxygen sensor. The present application furthermore relates to an electronic device comprising at least one compound according to the application.

[0251] Electronic device means a device comprising an anode, a cathode and at least one layer, wherein the layer comprises at least one organic or organometallic compound. Thus, an electronic device according to the application comprises an anode, a cathode and at least one layer comprising at least one metal complex according to the application. Preferred electronic devices here are selected from the group consisting of organic electroluminescent devices (OLED, PLED), organic infrared electroluminescent sensors, organic integrated circuits (O-IC), organic field effect transistors (O-FET), organic thin-film transistors (O-TFT), organic light-emitting transistors (O-LET), organic solar cells (O-SC) which means pure organic solar cells and dye-sensitised solar cells (DSC) (battery), organic optical detectors, organic photoreceptors, organic quenching field devices (O-FQD), light-emitting electrochemical cells (LEC), oxygen sensors or organic laser diodes (O-laser), said devices comprising at least one metal complex according to the application in at least one layer. Particularly preferred are organic electroluminescent devices. Active components are generally organic or inorganic materials which are introduced between anode and cathode, such as charge-injection, charge-transport or charge-blocking materials, but especially light-emitting materials and matrix materials. The compounds according to the application exhibit particularly good properties as light-emitting materials in organic electroluminescent devices. Organic electroluminescent devices are therefore one preferred embodiment of the present application. Furthermore, the compounds according to the application can be used for the generation of singlet oxygen or in photocatalysis. Battery)), organic optical detectors, organic photoreceptors, organic quenching field devices (O-FQD), light-emitting electrochemical cells (LEC), oxygen sensors or organic laser diodes (O-laser), said devices comprising at least one metal complex according to the application in at least one layer. Particularly preferred are organic electroluminescent devices. Active components are generally organic or inorganic materials which are introduced between anode and cathode, such as charge-injection, charge-transport or charge-blocking materials, but especially light-emitting materials and matrix materials. The compounds according to the application exhibit particularly good properties as light-emitting materials in organic electroluminescent devices. Organic electroluminescent devices are therefore one preferred embodiment of the present application. Furthermore, the compounds according to the application can be used for the generation of singlet oxygen or in photocatalysis.

[0252] The organic electroluminescent device comprises a cathode, an anode and at least one light-emitting layer. In addition to these layers, it can also comprise further layers, such as in each case one or more hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, exciton-blocking layers, electron-blocking layers, charge-generation layers and / or organic or inorganic p / n junctions. One or more hole-transport layers here can be p-doped, for example, with metal oxides such as Mo03or W03or with (per)fluorinated electrophilic aromatic compounds, and / or one or more electron-transport layers can be n-doped. An interlayer with, for example, exciton-blocking function and / or for controlling the charge balance in the electroluminescent device can likewise be introduced between two light-emitting layers. It should be noted, however, that not all of these layers necessarily have to be present.

[0253] The organic electroluminescent device here can comprise one emitting layer or a plurality of emitting layers. If a plurality of emitting layers is present, these preferably together have a plurality of emission peaks between 380 nm and 750 nm, resulting in an overall white emission, i.e. a plurality of luminescent compounds capable of fluorescing or phosphorescing are used in the emitting layer. A three-layer system is particularly preferred, in which the three layers show blue, green and orange or red emission (for the basic structure, see for example WO 2005 / 011013), or a system having more than three emitting layers. It can also be a hybrid system, in which one or more layers fluoresce and one or more other layers phosphoresce. The white-emitting organic electroluminescent device can be used for lighting applications or, together with color filters, for full-color displays. The white-emitting OLED can also be realized by tandem OLEDs. Furthermore, the white-emitting OLED can also be realized by two or more emitters emitting different colors of light, and in which at least one is a compound according to the application present in the emitting layer, so that the light emitted by the individual emitters combines to white light.

[0254] In a preferred embodiment of the application, the organic electroluminescent device comprises a metal complex according to the application as luminescent compound in one or more emitting layers.

[0255] Many compounds according to the application emit in the red spectral region. However, by appropriate choice of ligands and substitution pattern, it is possible on the one hand to shift the emission into the infrared region, and on the other hand also to blue-shift the emission, preferably into the orange, yellow or green region, and also the blue region.

[0256] If the metal complex according to the application is used as luminescent compound in an emitting layer, it is preferably used in combination with one or more matrix materials, where the terms "matrix material" and "host material" are used synonymously hereinafter. The mixture of the metal complex according to the application and the matrix material comprises 1 to 99 % by weight, preferably 1 to 90 % by weight, particularly preferably 3 to 40 % by weight, in particular 5 to 25 % by weight, of the metal complex according to the application, based on the mixture comprising the emitter and the matrix material as a whole. Correspondingly, the mixture comprises 99.9 to 1 % by weight, preferably 99 to 10 % by weight, particularly preferably 97 to 60 % by weight, in particular 95 to 75 % by weight, of the matrix material, based on the mixture comprising the emitter and the matrix material as a whole.

[0257] The matrix material used can generally be all materials known from the prior art for this purpose. The triplet level of the matrix material is preferably higher than the triplet level of the emitter.

[0258] Suitable matrix materials for the compounds according to the present application are ketones, phosphinoxides, sulfoxides and sulfones, such as according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680, triaryl amines, carbazole derivatives, such as CBP (N,N-dicarbazolylbiphenyl), m-CBP or carbazole derivatives disclosed in WO 2005 / 039246, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or US 2009 / 0134784, indolocarbazole derivatives, such as according to WO 2007 / 063754 or WO 2008 / 056746, indenocarbazole derivatives, such as according to WO 2010 / 136109 or WO 2011 / 000455, azacarbazoles, such as according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160, ambipolar matrix materials, such as according to WO 2007 / 137725, silanes, such as according to WO 2005 / 111172, azaboroles or borates, such as according to WO 2006 / 117052, diazasilole derivatives, such as according to WO 2010 / 054729, diazaphosphole derivatives, such as according to WO 2010 / 054730, triazine derivatives, such as according to WO 2010 / 015306, WO 2007 / 063754 or WO 2008 / 056746, zinc complexes, such as according to EP 652273 or WO 2009 / 062578, dibenzofuran derivatives, such as according to WO 2009 / 148015 or WO 2015 / 169412, or bridged carbazole derivatives, such as according to US 2009 / 0136779, WO 2010 / 050778, WO 2011 / 042107 or WO 2011 / 088877.

[0259] For solution-processed OLEDs, suitable matrix materials are also polymers, such as according to WO 2012 / 008550 or WO 2012 / 048778, or oligomers or dendrimers, such as according to Journal of Luminescence 183 (2017), 150-158.

[0260] It can furthermore be preferred to use a plurality of different matrix materials, in particular at least one electron-conducting matrix material and at least one hole-conducting matrix material, in admixture. Preferred combinations are, for example, the use of aromatic ketones, triazine derivatives or phosphine oxide derivatives with triarylamine derivatives or carbazole derivatives as mixed matrix for the metal complexes according to the application. It is likewise preferred to use mixtures of charge-transporting matrix materials with electrically inert matrix materials which do not participate or do not substantially participate in charge transport (so-called "wide-bandgap hosts"), as described, for example, in WO 2010 / 108579 or WO 2016 / 184540. It is likewise preferred to use two electron-transporting matrix materials, for example a triazine derivative and a lactam derivative, as described, for example, in WO 2014 / 094964.

[0261] Examples of compounds which are suitable as matrix materials for the compounds according to the application are described below.

[0262] Examples of compounds which are suitable as matrix materials for the compounds according to the application are described below.

[0263] Examples of triazines and pyrimidines which can be used as electron-transporting matrix materials are as follows:

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276]

[0277] Examples of lactams which can be used as electron-transporting matrix materials are as follows:

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285] Examples of ketones that can be used as electron transport matrix materials are as follows:

[0286]

[0287]

[0288]

[0289]

[0290]

[0291]

[0292] Examples of metal complexes that can be used as electron transport matrix materials are as follows:

[0293]

[0294]

[0295] Examples of phosphine oxides that can be used as electron transport matrix materials are as follows:

[0296]

[0297]

[0298] Examples of the most general indolocarbazole and indenocarbazole derivatives that can be used as hole or electron transport matrix materials depending on the substitution pattern are as follows:

[0299]

[0300]

[0301]

[0302]

[0303]

[0304] Examples of carbazole derivatives which can be used as hole or electron transport matrix materials depending on the substitution pattern are as follows:

[0305]

[0306]

[0307]

[0308] Examples of bridged carbazole derivatives which can be used as hole transport matrix materials are as follows:

[0309]

[0310]

[0311]

[0312]

[0313] Examples of bis-carbazole derivatives which can be used as hole transport matrix materials are as follows:

[0314]

[0315]

[0316]

[0317]

[0318] Examples of amines which can be used as hole transport matrix materials are as follows:

[0319]

[0320]

[0321]

[0322]

[0323] Examples of materials which can be used as wide band gap matrix materials are as follows:

[0324]

[0325]

[0326] It is furthermore preferred to use mixtures of two or more triplet emitters, in particular two or three triplet emitters, with one or more matrix materials. Here the triplet emitter with the shorter-wave emission spectrum serves as co-host for the triplet emitter with the longer-wave emission spectrum. Thus, for example, the metal complex according to the application can be combined with a metal complex which emits at a shorter wavelength, for example blue, green or yellow light, as co-host. The metal complex according to the application can also be used, for example, as co-host for a triplet emitter which emits at a longer wavelength, for example as co-host for a red-emitting triplet emitter. It can also be preferred here that both the metal complex which emits at a shorter wavelength and the metal complex which emits at a longer wavelength are compounds according to the application. In the case of mixtures of three triplet emitters, the preferred embodiment is that two serve as co-hosts and one as emitter. These triplet emitters preferably have green, yellow and red or blue, green and orange emission colors.

[0327] A preferred mixture in the light-emitting layer comprises an electron-transporting host material, a so-called "wide-bandgap" host material, which does not participate in or to a significant extent in the charge transport in the layer due to its electronic properties; a co-dopant, which is a triplet emitter which emits at a shorter wavelength than the compound according to the application; and the compound according to the application.

[0328] A further preferred mixture in the light-emitting layer comprises an electron-transporting host material, a so-called "wide-bandgap" host material, which does not participate in or to a significant extent in the charge transport in the layer due to its electronic properties; a hole-transporting host material; a co-dopant, which is a triplet emitter which emits at a shorter wavelength than the compound according to the application; and the compound according to the application.

[0329] Examples of suitable triplet emitters which can be used as co-dopants for the compounds according to the application are described in the following table.

[0330]

[0331]

[0332]

[0333]

[0334]

[0335]

[0336]

[0337]

[0338]

[0339]

[0340] Also suitable are the following polypyridyl complexes having the following CAS numbers:

[0341]

[0342]

[0343]

[0344]

[0345] Depending on the choice of metal and the exact structure of the ligand, the metal complexes according to the application can also be used in electronic devices for other functions, for example as hole-transport material in a hole-injection or hole-transport layer, as charge-generation material, as electron-blocking material, as hole-blocking material or as electron-transport material in an electron-transport layer, for example. If the metal complex according to the application is an aluminium complex, this is preferably used in an electron-transport layer. The metal complexes according to the application can likewise be used as matrix material for other phosphorescent metal complexes in an emission layer.

[0346] The cathode preferably comprises a metal, a metal alloy or a multilayer structure comprising a plurality of metals having a low work function, for example an alkali earth metal, an alkali metal, a main group metal or a lanthanide (for example Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys comprising an alkali metal or an alkali earth metal and silver, for example an alloy comprising magnesium and silver. In the case of a multilayer structure, it is also possible to use, in addition to the metal, other metals having a relatively high work function, for example Ag, in which case combinations of metals are generally used, for example Mg / Ag, Ca / Ag or Ba / Ag. It can also be preferred to introduce a thin intermediate layer of a material having a high dielectric constant between the metal cathode and the organic semiconductor. Suitable for this purpose are, for example, alkali metal or alkali earth metal fluorides, and also the corresponding oxides or carbonates (for example LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.). Organic alkali metal complexes, for example Liq (lithium quinolate), are likewise suitable for this purpose. The layer thickness of this layer is preferably from 0.5 nm to 5 nm.

[0347] The anode preferably comprises a material having a high work function. The anode preferably has a work function greater than 4.5 eV versus vacuum. Suitable for this purpose are, on the one hand, metals having a high redox potential, for example Ag, Pt or Au. On the other hand, metal / metal oxide electrodes (for example Al / Ni / NiO x , Al / PtOx For some applications at least one electrode must be transparent or partially transparent to facilitate the emission of organic materials (O-SC) or the coupling-out of light (OLEDs / PLEDs, O-lasers). 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, such as PEDOT, PANI or derivatives of these polymers. Furthermore preferred is the application of a p-doped hole transport material to the anode as a hole injection layer, wherein suitable p-dopants are metal oxides, such as MoO3or WO3, or (per)fluorinated electron-deficient aromatic compounds. Other suitable p-dopants are HAT-CN (hexacyanohexaazatriphenylene) or the compound NPD9 from Novaled. Layers of this type simplify the hole injection in materials having a low HOMO, i.e. a large HOMO value.

[0348] In further layers it is generally possible to use all materials as used for the layers according to the prior art, and the person skilled in the art will be able to combine each of these materials with the materials according to the application in electronic devices without inventive step.

[0349] The devices are structured accordingly (depending on the application), contact points are provided and finally hermetically sealed, since the lifetime of these devices is drastically shortened in the presence of water and / or air.

[0350] Furthermore preferred is an organic electroluminescent device, characterized in that one or more layers are applied by a sublimation process, wherein the material is vapor-deposited in a vacuum sublimation apparatus at an initial pressure of typically less than 10 -5 mbar, preferably less than 10 -6 mbar. The initial pressure can also be lower or higher, for example less than 10 -7 mbar.

[0351] Also preferred is an organic electroluminescent device, characterized in that one or more layers are applied by an OVPD (organic vapor phase deposition) process or by means of carrier gas sublimation, wherein the material is applied at a pressure of 10 -5 mbar to 1 bar. A particular example of this method is the OVJP (organic vapor jet printing) method, wherein the material is applied directly through a nozzle and is thus structured.

[0352] Furthermore, preference is given to an organic electroluminescent device, characterized in that one or more layers are produced from solution, for example by spin coating, or by any desired printing method, such as screen printing, flexographic printing, offset printing or nozzle printing, but particularly preferably LITI (light induced thermal imaging, thermal transfer printing) or inkjet printing. For this purpose, soluble compounds are required, which are obtained, for example, by suitable substitution. In a preferred embodiment of the application, the layer comprising the compounds according to the application is applied from solution.

[0353] By applying one or more layers from solution and by applying one or more further layers by vapor deposition, the organic electroluminescent device can also be produced as a hybrid system. Thus, for example, a light-emitting layer comprising the metal complex according to the application and a matrix material can be applied from solution and a hole-blocking layer and / or an electron-transporting layer can be applied thereon by vacuum vapor deposition.

[0354] These methods are generally known to the person skilled in the art and can be applied without difficulty to the organic electroluminescent device comprising the compounds of the formula (1) or (2) or the preferred embodiments detailed above.

[0355] The electronic device, in particular the organic electroluminescent device, according to the application is distinguished from the prior art by one or more of the following advantages:

[0356] 1. The compounds according to the application have a very high photoluminescence quantum yield. When used in an organic electroluminescent device, this leads to excellent efficiency.

[0357] 2. The compounds according to the application have a very short luminescence lifetime. When used in an organic electroluminescent device, this leads to improved roll-off behavior and, by avoiding non-radiative relaxation channels, to a higher luminescence quantum yield.

[0358] These above-mentioned advantages are not accompanied by a deterioration of other electronic properties.

[0359] The application is explained in more detail by the following examples, without thereby wishing to be limited thereto. The person skilled in the art will be able to use the present description to produce further electronic devices according to the application without inventive step and thus to carry out the application within the full scope claimed. Examples:

[0360] The following syntheses were carried out in dry solvents under an atmosphere of protective gas, unless stated otherwise. The metal complexes were additionally handled in the dark or under yellow light. The solvents and reagents can be purchased from, for example, Sigma-ALDRICH or A BCR. The respective number in square brackets or the number indicated for an individual compound refers to the CAS number of the compound known from the literature.

[0361] Synthesis of structural unit B

[0362] Example B1 :

[0363]

[0364] A mixture of 23.8 g (100 mmol) of 4,6-dibromopyrimidine [36847-10-6], 41.3 g (200 mmol) of (4-chloronaphthalen-1-yl)boronic acid [147102-97-4], 63.6 g (600 mmol) of sodium carbonate, 5.8 g (5 mmol) of tetrakis(triphenylphosphine)palladium(0) [14221-01-3], 800 ml of toluene, 300 ml of ethanol and 700 ml of water was heated under reflux for 24 hours. After cooling, the organic phase was separated, washed twice with 300 ml of water and once with 200 ml of a saturated NaCI solution, filtered through a bed of celite and the filtrate was evaporated to dryness. The residue was purified twice by recrystallization from acetonitrile. Yield: 20.5 g (51 mmol), 51 %; purity: 95 %, according to H-NMR. 1 H-NMR.

[0365] Example B204:

[0366]

[0367] Structural unit B204 can be prepared analogously to the procedure for B1, using 4,6-dibromo-5-methylpyrimidine [83941-93-9] instead of 4,6-dibromopyrimidine and 4-chlorophenylboronic acid [1679-18-1] instead of (4-chloronaphthalen-1-yl)boronic acid. Yield: 55 %.

[0368] Example B2:

[0369]

[0370] A 4 I four-necked flask with reflux condenser, argon blanket, precision glass stirrer and internal thermometer, which was inertized with argon, was charged with 134 g of 4-chlorophenylboronic acid (860 mmol) [1679-18-1], 250.0 g of 5-bromo-2-iodopyridine (880 mmol) [223463-13-6] and 232.7 g of potassium carbonate (1.68 mol) [127-08-2] and 1500 ml of acetonitrile and 1000 ml of absolute ethanol were added. 100 g of glass beads (diameter 3 mm) were added and the suspension was homogenized for 5 minutes. Then 5.8 g of bis(triphenylphosphine)palladium(II) chloride [13965-03-2] were added. The reaction mixture was heated under reflux with vigorous stirring overnight. After cooling, the solvent was removed in a rotary evaporator and the residue was worked up by extraction with toluene and water in a separatory funnel. The organic phase was washed twice with 500 ml of water and once with 300 ml of saturated sodium chloride solution, dried over anhydrous sodium sulfate and the solvent was then removed in vacuo. The residue was dissolved in dichloromethane and filtered through a glass frit of silica gel. The silica gel bed was rinsed twice with 500 ml of dichloromethane each time. To the filtrate, 800 ml of ethanol were added and the dichloromethane was stripped off in a rotary evaporator to 500 mbar. After removal of the dichloromethane in a rotary evaporator, the solid precipitated from the residual ethanol, was suction filtered and washed with ethanol. The yellow solid obtained was recrystallized from 800 ml of acetonitrile under reflux to give a beige solid. Yield: 152.2 g (567.0 mmol), 66%; purity: about 95% according to H-NMR. 1 H-NMR.

[0371] Example B3:

[0372]

[0373] The building block B3 can be prepared analogously to the procedure described for B2, using 2,4-dibromopyridine [58530-53-3] instead of 5-bromo-2-iodopyridine. Yield: 54%.

[0374] Example B4:

[0375]

[0376] A 4 I four-necked flask with reflux condenser, precision glass stirrer, heating bath and argon connection, which was inertized with argon, was charged with 162.0 g (600 mmol) of B2, 158.0 g (622 mmol) of bis(pinacolato)diboron [73183-34-3], 180.1 g (1.83 mol) of potassium acetate [127-08-2] and 8.9 g (12.1 mmol) of trans-dichlorobis(tricyclohexylphosphine)palladium(II) [29934-17-6] and 2200 ml of 1,4-dioxane were added. The reaction mixture was heated under reflux with vigorous stirring for 3 days. After cooling, the solvent was removed in a rotary evaporator and the residue was worked up by extraction with toluene and water in a separatory funnel. The organic phase was washed twice with 500 ml of water and once with 300 ml of saturated sodium chloride solution, dried over anhydrous sodium sulfate and the solvent was then removed in vacuo. The residue was dissolved in dichloromethane and filtered through a glass frit of silica gel. The silica gel bed was rinsed twice with 500 ml of dichloromethane each time. To the filtrate, 800 ml of ethanol were added and the dichloromethane was stripped off in a rotary evaporator to 500 mbar. After removal of the dichloromethane in a rotary evaporator, the solid precipitated from the residual ethanol, was suction filtered and washed with ethanol. The yellow solid obtained was recrystallized from 800 ml of acetonitrile under reflux to give a beige solid. Yield: 152.2 g (567.0 mmol), 66%; purity: about 95% according to H-NMR. Alk. 100 g of glass beads (diameter 3 mm) were added, the reaction mixture was inerted with argon and stirred under reflux for 24 hours. After cooling, the solvent was removed in vacuo and the resulting residue was treated by extraction in a separatory funnel with 1000 ml of ethyl acetate and 1500 ml of water. The organic phase was washed once with 500 ml of water and once with 300 ml of saturated sodium chloride solution, dried over anhydrous sodium sulfate and filtered through a glass frit packed with silica gel. The silica gel bed was rinsed twice with 500 ml of ethyl acetate and the resulting filtrate was evaporated in vacuo. The resulting brown solid was recrystallized from 1000 ml of n-heptane under reflux to give a beige solid. Yield: 150.9 g (478 mmol), 80%; purity: 97%, according to HPLC. 1 H-NMR.

[0377] Example B5:

[0378]

[0379] Structural unit B5 can be prepared analogously to the procedure described for B4, starting from compound B3. 12 mmol of [1,1 '-bis(diphenylphosphino)ferrocene]dichloropalladium(II) complex with dichloromethane [95464-05-4] instead of 12.1 mmol of trans-dichlorobis(tricyclohexylphosphine)palladium(II). Yield: 75%.

[0380] Example B6:

[0381]

[0382] Into a 2 1 four necked flask with reflux condenser, argon blanket, precision glass stirrer and internal thermometer, which was inertized with argon, 31.5 g (100 mmol) of B4, 28.4 g of 5-bromo-2-iodopyridine (100 mmol) [223463-13-6] and 34.6 g of potassium carbonate (250 mmol) were weighed in and 500 ml of acetonitrile and 350 ml of absolute ethanol were added. 30 g of glass beads (diameter 3 mm) were added and the suspension was homogenized for 5 minutes. Then 702 mg of bis(triphenylphosphine)palladium(II) chloride (1 mmol) [13965-03-2] were added. The reaction mixture was warmed up under reflux with vigorous stirring overnight. After cooling, the solvent was removed in a rotary evaporator and the residue was worked up by extraction in a separatory funnel with toluene and water. The organic phase was washed twice with 500 ml of water and once with 300 ml of saturated sodium chloride solution, dried over anhydrous sodium sulfate and the solvent was then removed in vacuo. The residue was dissolved in dichloromethane and filtered through a glass frit of silica gel, which was rinsed twice with 200 ml of dichloromethane / ethyl acetate 1 : 1 each time, and the dichloromethane was stripped off in a rotary evaporator to 500 mbar. During the removal of the dichloromethane in the rotary evaporator, the solid precipitated from the residual ethyl acetate, was suction filtered and washed with ethyl acetate. The crude product was recrystallized again from ethyl acetate. Yield: 24.2 g (72 mmol), 72%; purity: about 95%, according to H-NMR. 1 H-NMR.

[0383] Example B7:

[0384] Analogous procedure to the one described for B6. Recrystallization from acetonitrile instead of ethyl acetate. Yield: 68%.

[0385]

[0386] Example B8:

[0387]

[0388] Into a 2 1 four necked flask with reflux condenser, argon blanket, precision glass stirrer and internal thermometer, which was inertized with argon, 31.5 g (100 mmol) of B4, 28.4 g of 5-bromo-2-iodopyridine (100 mmol) [223463-13-6] and 34.6 g of potassium carbonate (250 mmol) were weighed in and 500 ml of acetonitrile and 350 ml of absolute ethanol were added. 30 g of glass beads (diameter 3 mm) were added and the suspension was homogenized for 5 minutes. Then 702 mg of bis(triphenylphosphine)palladium(II) chloride (1 mmol) [13965-03-2] were added. The reaction mixture was warmed up under reflux with vigorous stirring overnight. After cooling, the solvent was removed in a rotary evaporator and the residue was worked up by extraction in a separatory funnel with toluene and water. The organic phase was washed twice with 500 ml of water and once with 300 ml of saturated sodium chloride solution, dried over anhydrous sodium sulfate and the solvent was then removed in vacuo. The residue was dissolved in dichloromethane and filtered through a glass frit of silica gel, which was rinsed twice with 200 ml of dichloromethane / ethyl acetate 1 : 1 each time, and the dichloromethane was stripped off in a rotary evaporator to 500 mbar. During the removal of the dichloromethane in the rotary evaporator, the solid precipitated from the residual ethyl acetate, was suction filtered and washed with ethyl acetate. The crude product was recrystallized again from ethyl acetate. Yield: 24.2 g (72 mmol), 72%; purity: about 95%, according to H-NMR. The mixture was heated under reflux for 16 hours. The solvent was removed in a rotary evaporator and the residue was worked up by extraction in a separatory funnel with toluene and water. The organic phase was washed twice with 500 ml of water and once with 300 ml of saturated sodium chloride solution, dried over anhydrous sodium sulfate and the solvent was then removed in vacuo. The residue was dissolved in dichloromethane and filtered through a glass frit of silica gel, which was rinsed twice with 200 ml of dichloromethane / ethyl acetate 1 : 1 each time, and the dichloromethane was stripped off in a rotary evaporator to 500 mbar. During the removal of the dichloromethane in the rotary evaporator, the solid precipitated from the residual ethyl acetate, was suction filtered and washed with ethyl acetate. The crude product was recrystallized again from ethyl acetate. Yield: 24.2 g (72 mmol), 72%; purity: about 95%, according to H-NMR. The black residue was extracted with 1000 ml of ethyl acetate and 500 ml of water in a separatory funnel. The organic phase was washed once with 300 ml of water and once with 150 ml of saturated sodium chloride solution, and then filtered through a silica gel bed. The silica gel was washed twice with 250 ml of ethyl acetate. The filtrate was dried over sodium sulfate and evaporated to 150 ml. Then 400 ml of n-heptane was added, and the remaining ethyl acetate was vaporized to 200 mbar in a rotary evaporator at a bath temperature of 55 °C. During the removal of ethyl acetate in the rotary evaporator, a solid precipitated from the residual n-heptane. The precipitated solid was heated under reflux for 30 min, cooled, filtered off, and washed twice with 30 ml of n-heptane each time. Yield: 37.8 g (78 mmol), 78%. Purity: approx. 98%, according to 1 H NMR.

[0389] The following compounds can be prepared similarly:

[0390]

[0391]

[0392]

[0393] Example B18:

[0394]

[0395] 34.6 g (100 mmol) of B6, 25.4 g (100 mmol) of bis(pinacolyl)diborane [73183-34-3], 29.4 g (300 mol) of potassium acetate [127-08-2], and 1.63 g (2 mmol) of the complex of [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride with dichloromethane [95464-05-4] were weighed into a 1000 ml four-necked flask equipped with a reflux condenser, a precision glass stirrer, a heating bath, and argon gas connection. 500 ml of 1,4-di(B6) ... Alkan. 30 g glass beads (diameter 3 mm) were added and the reaction mixture was inertized with argon and stirred under reflux for 24 h. After cooling, the solvent was removed in vacuo and the residue was worked up by extraction with 600 ml ethyl acetate and 600 ml water in a separation funnel. The organic phase was washed once with 500 ml water and once with 300 ml saturated sodium chloride solution, dried over anhydrous sodium sulfate and filtered through a glass frit packed with silica gel. The silica gel bed was rinsed twice with 500 ml ethyl acetate and the resulting filtrate was evaporated in vacuo. To the resulting brown solid, 500 ml n-heptane was added and the formed suspension was boiled under reflux for 1 h. The solid was suction filtered and washed with 50 ml n-heptane to yield a beige solid. Yield: 34.6 g (89 mmol), 89%; purity: 98%, according to HPLC. 1 H-NMR.

[0396] Example B19:

[0397]

[0398] Analogous to the procedure of Example B18. B7 was used instead of B6 as starting material. Yield: 82%.

[0399] Example B20:

[0400]

[0401] A mixture of 48.4 g (100 mmol) of B8, 56.6 g (200 mmol) of 1-bromo-2- iodobenzene [583-55-1], 63.6 g (600 mmol) of sodium carbonate, 5.8 g (5 mmol) of tetrakis(triphenylphosphine)palladium(0) [14221-01-3], 1000 ml of 1,2-dimethoxyethane and 500 ml of water was heated under reflux for 60 h. After cooling, the solid that had precipitated out was suction filtered and washed 3 times with 100 ml of ethanol. The crude product was dissolved in 1000 ml of dichloromethane and filtered through a silica gel bed that had been pre-slurried with dichloromethane. The silica gel was rinsed 3 times with 100 ml of ethyl acetate each. The dichloromethane was removed in a rotary evaporator at a bath temperature of 50 °C to 500 mbar. During the removal of the dichloromethane in the rotary evaporator, the solid precipitated from the remaining ethyl acetate. The solid that had precipitated out was filtered off and washed 2 times with 20 ml of ethyl acetate. The resulting solid was recrystallized again from 2000 ml of boiling ethyl acetate. Yield: 29.3 g (54 mmol), 54%; purity: 97%, according to HPLC. 1 H-NMR.

[0402] The following compounds can be prepared analogously, wherein solvents such as ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol or methanol can be used for recrystallization. Thermal extraction can also be performed with these solvents or purification can be performed by silica gel chromatography on an automated column (Torrent from Axel Semrau).

[0403]

[0404]

[0405] Example B32:

[0406]

[0407] A mixture of 18.1 g (100 mmol) of 6-chlorotetralone [26673-31-4], 16,5 g (300 mmol) of propargylamine [2450-71-7], 796 mg (2 mmol) of sodium tetrachloroaurate(III) dihydrate and 200 ml of ethanol was stirred in an autoclave at 120°C for 24 hours. After cooling, the ethanol was removed in vacuo, the residue was dissolved in 200 ml of ethyl acetate, the solution was washed three times with 200 ml of water, once with 100 ml of saturated sodium chloride solution, dried over magnesium sulfate and then filtered off from the latter through a pre-slurried bed of silica gel. After removal of the ethyl acetate in vacuo, the residue was chromatographed on silica gel with n-heptane / ethyl acetate (1 :2 vv). Yield: 9.7 g (45 mmol), 45%. Purity: about 98%, according to H-NMR. 1 H-NMR.

[0408] Example B33:

[0409]

[0410] A mixture of 25.1 g (100 mmol) of 2,5-dibromo-4-methylpyridine [3430-26-0], 15.6 g (100 mmol) of 4-chlorophenylboronic acid [1679-18-1], 27.6 g (200 mmol) of potassium carbonate, 1.57 g (6 mmol) of triphenylphosphine [603-35-0], 676 mg (3 mmol) of palladium(II) acetate [3375-31-3], 200 g of glass beads (diameter 3 mm), 200 ml of acetonitrile and 100 ml of ethanol was heated under reflux for 48 hours. After cooling, the solvent was removed in vacuo, 500 ml of toluene was added, the mixture was washed twice with 300 ml of water each time, once with 200 ml of saturated sodium chloride solution, dried over magnesium sulfate, filtered off through a bed of pre-slurried silica gel and the bed of silica gel was rinsed with 300 ml of toluene. After removal of the toluene in vacuo, the product was recrystallized once from methanol / ethanol (1 :1 vv) and once from n-heptane. Yield: 17.3 g (61 mmol), 61%. Purity: about 95%, according to H-NMR. 1 H-NMR.

[0411] Example B34:

[0412]

[0413] B34 can be prepared analogously to the procedure described in relation to Example B33. To this end, 4-bromo-6-tert-butylpyrimidine [19136-36-8] is used instead of 2,5-dibromo-4-methylpyridine. Yield: 70%.

[0414] Example B35:

[0415]

[0416] A mixture of 28.3 g (100 mmol) of B33, 12.8 g (105 mmol) of phenylboronic acid, 31.8 g (300 mmol) of sodium carbonate, 787 mg (3 mmol) of triphenylphosphine, 225 mg (1 mmol) of palladium(II) acetate, 300 ml of toluene, 150 ml of ethanol and 300 ml of water was heated under reflux for 48 hours. After cooling, the mixture was expanded with 300 ml of toluene, the organic phase was separated off, washed once with 300 ml of water, once with 200 ml of saturated sodium chloride solution and dried over magnesium sulfate. After removal of the solvent, the residue was chromatographed on silica gel (toluene / ethyl acetate, 9:1 vv). Yield: 17.1 g (61 mmol), 61%. Purity: about 97%, according to H-NMR. 1 H-NMR.

[0417] The following compounds can be synthesized analogously:

[0418]

[0419] Example B39:

[0420]

[0421] A mixture of 164.2 g (500 mmol) of 2-(1,1,2,2,3,3-hexamethylindan-5-yl)-4,4,5,5- tetramethyl-1,3,2-dioxaborinane [152418-16-9] (boronic acid can be used analogously), 142.0 g (500 mmol) of 5-bromo-2-iodopyridine [223463-13-6], 159.0 g (1.5 mol) of sodium carbonate, 5.8 g (5 mmol) of tetrakis(triphenylphosphine)palladium(0), 700 ml of toluene, 300 ml of ethanol and 700 ml of water was heated under reflux for 16 hours under vigorous stirring. After cooling, 1000 ml of toluene were added, the organic phase was separated off and the aqueous phase was then extracted with 300 ml of toluene. The combined organic phases were washed once with 500 ml of a saturated sodium chloride solution. The organic phase was dried over sodium sulfate and, after removal of the solvent in vacuo, the crude product was recrystallized twice from about 300 ml of EtOH. Yield: 130.8 g (365 mmol), 73%. Purity: about 95%, according to H-NMR. 1 H-NMR.

[0422] The following compounds can be prepared analogously, wherein the pyridine derivative used is generally 5-bromo-2-iodopyridine ([223463-13-6]), which is not shown separately in the table below: only the different pyridine derivatives are explicitly shown in the table. Solvents such as ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol or methanol can be used for recrystallization. Thermal extraction can also be carried out with these solvents, or purification can be carried out by silica gel chromatography on an automated column (Torrent from Axel Semrau).

[0423]

[0424]

[0425]

[0426] Example B48:

[0427] Variant A:

[0428]

[0429] 35.8 g (100 mmol) of B39, 25.4 g (100 mmol) of bis(pinacolyl)diborane [73183-34-3], 49.1 g (500 mmol) of potassium acetate, 1.5 g (2 mmol) of a complex of 1,1-bis(diphenylphosphino)ferrocene palladium(II) dichloromethane [95464-05-4], 200 g of glass beads (3 mm in diameter), and 700 ml of 1,4-diphenylphosphine dichloride... A mixture of alkylene and 700 ml toluene was heated under reflux for 16 hours. After cooling, the suspension was filtered through a diatomaceous earth bed, and the solvent was removed under vacuum. The black residue was dissolved in 1000 ml of hot n-heptane, cyclohexane, or toluene, filtered hot through a diatomaceous earth bed, and then evaporated to about 200 ml, during which time the product began to crystallize. Alternatively, it could be extracted with ethyl acetate. Crystallization was completed overnight in a refrigerator, the crystals were filtered off, and washed with a small amount of n-heptane. A second product fraction could be obtained from the mother liquor. Yield: 31.6 g (78 mmol), 78%. Purity: approximately 95%, according to 1 H-NMR.

[0430] Variant B: Reaction of aryl chlorides

[0431] For example, for the preparation of variant A, but with 2 mmol of S-Phos[657408-07-6] and 1 mmol of palladium(II) acetate instead of the complex of 1,1-bis(diphenylphosphino)ferrocene palladium(II) dichloride with dichloromethane.

[0432] The following compounds can be prepared similarly, wherein cyclohexane, toluene, acetonitrile, or a mixture of the solvents can be used instead of n-heptane for purification:

[0433]

[0434]

[0435]

[0436]

[0437]

[0438]

[0439] Example B80:

[0440]

[0441] A mixture of 28.1 g (100 mmol) of B49, 28.2 g (100 mmol) of 1-bromo-2- iodobenzene [583-55-1], 31.8 g (300 mmol) of sodium carbonate, 787 mg (3 mmol) of triphenylphosphine, 225 mg (1 mmol) of palladium(II) acetate, 300 ml of toluene, 150 ml of ethanol and 300 ml of water was heated under reflux for 24 hours. After cooling, the mixture was diluted with 500 ml of toluene, the organic phase was separated, washed once with 500 ml of water, once with 500 ml of saturated sodium chloride solution and dried over magnesium sulfate. After removal of the solvent, the residue was recrystallized from ethyl acetate / n-hexane or chromatographed on silica gel (toluene / ethyl acetate, 9:1 vv). Yield: 22.7 g (73 mmol), 73%. Purity: about 97%, according to H-NMR. 1 H-NMR.

[0442] The following compounds can be prepared analogously, wherein solvents such as ethyl acetate, cyclohexane, toluene, acetonitrile, n-hexane, ethanol or methanol can be used for recrystallization. Thermal extraction with these solvents is also possible, or purification by silica gel chromatography on an automated column (Torrent from Axel Semrau) is possible.

[0443]

[0444]

[0445]

[0446]

[0447] Example B106:

[0448]

[0449] Prepared according to G. Markopoulos et al., Angew. Chem., Int. Ed., 2012, 51, 12884.

[0450]

[0451] According to the procedure of JP 2000-169400. 5.7 g (105 mmol) of sodium methoxide were added in portions to a solution of 36.6 g (100 mmol) of 1,3-bis(2-bromophenyl)-2- propen-1 -one [126824-93-9] (step a)) in 300 ml of dry acetone and the mixture was stirred at 40 °C for 12 h. The solvent was removed in vacuo and the residue was dissolved in ethyl acetate, washed three times with 200 ml of water each, twice with 200 ml of saturated sodium chloride solution each and dried over magnesium sulfate. The oil obtained after removal of the solvent in vacuo was subjected to flash chromatography (Torrent CombiFlash, Axel Semrau). Yield: 17.9 g (44 mmol), 44%. Purity: ca. 97%, according to H-NMR. 1 H-NMR.

[0452]

[0453] At 0 °C 2.4 g (2.4 mmol) of anhydrous copper (I) chloride [7758-89-6] were added to a solution of 2-chlorophenylmagnesium bromide (200 mmol) [36692-27-0] in 200 ml of di-n-butyl ether and the mixture was stirred for another 30 min. Then a solution of 40.6 g (100 mmol) of the product of step b) in 200 ml of toluene was added dropwise over the course of 30 min and the mixture was stirred at 0 °C for another 5 h. The reaction mixture was quenched by careful addition of 100 ml of water and then 220 ml of 1 N hydrochloric acid. The organic phase was separated, washed twice with 200 ml of water each, once with 200 ml of saturated sodium bicarbonate solution, once with 200 ml of saturated sodium chloride solution and dried over magnesium sulfate. The oil obtained after removal of the solvent in vacuo was filtered through silica gel with toluene. The crude product obtained in this way was used without further purification for the further reactions. Yield: 49.8 g (96 mmol), 96%. Purity: ca. 90-95%, according to H-NMR. 1 H-NMR.

[0454]

[0455] To a solution of 51.9 g (100 mmol) of the product of step c) in 500 ml dichloromethane (DCM) cooled to 0°C was added 1.0 ml trifluoromethanesulfonic acid, followed by 50 g of phosphorous pentoxide in several portions. The mixture was allowed to warm to room temperature and stirred for another 2 hours. The supernatant was decanted from the phosphorous pentoxide, which was suspended in 200 ml DCM and the supernatant was decanted again. The combined DCM phases were washed twice with water and once with a saturated sodium chloride solution and dried over magnesium sulfate. The waxy material obtained after removal of the solvent in vacuo was subjected to flash chromatography (Torrent CombiFlash, Axel Semrau). Yield: 31.5 g (63 mmol), 63%, mixture of isomers. Purity: about 90-95%, according to1H-NMR. 1 H-NMR.

[0456]

[0457] A mixture of 25.0 g (50 mmol) of the product of step d), 2 g of Pd / C (10%), 200 ml of methanol and 300 ml of ethyl acetate was charged into a stirred autoclave under 3 bar of hydrogen and hydrogenated at 30°C until the hydrogen was completely absorbed. The mixture was filtered through a bed of diatomaceous earth which had been pre-slurried with ethyl acetate and the filtrate was evaporated to dryness. The oily material obtained in this way was subjected to flash chromatography (Torrent CombiFlash, Axel Semrau). Yield: 17.2 g (34 mmol), 68%. Purity: about 95%, according to1H-NMR, cis,cis isomer. 1 H-NMR, cis,cis isomer.

[0458] The following compounds can be prepared analogously.

[0459]

[0460]

[0461] Example B110:

[0462]

[0463] A mixture of 36.4 g (100 mmol) of 2,2'-(5-chloro-1,3-phenylene)-bis[4,4,5,5-tetramethyl-1,3,2-dioxaborolane [1417036-49-7], 65.2 g (210 mmol) of B80, 42.4 g (400 mmol) of sodium carbonate, 1.57 g (6 mmol) of triphenylphosphine, 500 mg (2 mmol) of palladium(II) acetate, 500 ml of toluene, 200 ml of ethanol and 500 ml of water was heated under reflux for 48 hours. After cooling, the mixture was diluted with 500 ml of toluene, the organic phase was separated, washed once with 500 ml of water, once with 500 ml of saturated sodium chloride solution and dried over magnesium sulfate. After removal of the solvent, the residue was chromatographed on silica gel (n-heptane / ethyl acetate 2:1 vv). Yield: 41.4 g (68 mmol), 68%. Purity: about 95%, according to H-NMR. 1 H-NMR.

[0464] The following compounds can be prepared analogously, wherein solvents such as ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol or methanol can be used for recrystallization. Thermal extraction with these solvents can also be performed, or purification can be performed by silica gel chromatography on an automated column (Torrent from Axel Semrau).

[0465]

[0466]

[0467]

[0468] Example B122:

[0469]

[0470] A mixture of 17.1 g (100 mmol) of 4-(2-pyridyl)phenol [51035-40-6] and 12.9 g (100 mmol) of diisopropylethylamine [7087-68-5] was stirred in 400 ml of dichloromethane at room temperature for 10 minutes. 6.2 ml (40 mmol) of 5-chloroisophthaloyl dichloride, dissolved in 30 ml of dichloromethane, were added dropwise and the reaction mixture was stirred at room temperature for 14 hours. Subsequently, 10 ml of water were added and the reaction mixture was transferred to a separating funnel. The organic phase was washed twice with 100 ml of water and once with 50 ml of saturated NaCI solution, dried over sodium sulfate and evaporated to dryness. Yield: 18.0 g (38 mmol), 95%. Purity: about 95%, according to H-NMR. 1 H-NMR.

[0471] The following compounds can be prepared analogously. If the starting materials used differ from those described in the procedure for B122, their amounts are indicated:

[0472]

[0473]

[0474]

[0475] Example B132:

[0476]

[0477] Example B132: 2.0 g (50 mmol) of sodium hydride (60% dispersion in paraffin oil) [7646-69-7] are suspended in 300 ml of THF, then 5.0 g (10 mmol) of B124 are added, and the suspension is stirred at room temperature for 30 minutes. Subsequently, 1.2 ml of iodomethane (50 mmol) [74-88-4] are added, and the reaction mixture is stirred at room temperature for 50 hours. 20 ml of a concentrated aqueous ammonia solution are added, the mixture is stirred for a further 30 minutes, and then the solvent is distilled off in vacuo. The residue is dissolved in 300 ml of dichloromethane, washed once with 200 ml of a 5% strength aqueous ammonia solution, twice with 100 ml of water each time, once with 100 ml of a saturated sodium chloride solution, then dried over magnesium sulfate. The dichloromethane is removed in vacuo, and the crude product is recrystallized from ethyl acetate / methanol. Yield: 4.3 g (8 mmol), 80%. Purity: ca. 98%, according to H-NMR. 1 H-NMR.

[0478] The following compounds can be prepared analogously:

[0479]

[0480]

[0481] Example B137:

[0482]

[0483] A mixture of 36.4 g (100 mmol) of 2,2'-(5-chloro-1,3-phenylene)bis[4,4,5,5-tetramethyl-1,3,2-dioxaborolane [1417036-49-7], 70.6 g (210 mmol) of B93, 42.4 g (400 mmol) of sodium carbonate, 2.3 g (2 mmol) of tetrakis(triphenylphosphine)palladium(0), 1000 ml of 1,2-dimethoxyethane and 500 ml of water was heated under reflux for 48 h. After cooling, the solid that had precipitated was suction filtered and washed twice with 20 ml of ethanol. The solid was dissolved in 500 ml of dichloromethane and filtered through a bed of celite. The filtrate was evaporated to 100 ml, then 400 ml of methanol were added and the solid that had precipitated was suction filtered. The crude product was recrystallized once from ethyl acetate. Yield: 43.6 g (70 mmol), 70%. Purity: about 96%, according to H-NMR. 1 H-NMR.

[0484] The following compounds can be prepared analogously, wherein solvents such as ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol or methanol can be used for recrystallization. Thermal extraction with these solvents is also possible, or purification can be carried out by silica gel chromatography on an automated column (Torrent from Axel Semrau).

[0485]

[0486]

[0487]

[0488] Example B151

[0489]

[0490] A mixture of 57.1 g (100 mmol) of B110, 25.4 g (100 mmol) of bis(pinacolato)diboron [73183-34-3], 49.1 g (500 mmol) of potassium acetate, 2 mmol of S-Phos [657408-07-6] and 1 mmol of palladium(II) acetate, 200 g of glass beads (diameter 3 mm) and 700 ml of 1,4-dioxane was heated under reflux for 48 h. After cooling, the solid that had precipitated was suction filtered and washed twice with 20 ml of ethanol. The solid was dissolved in 500 ml of dichloromethane and filtered through a bed of celite. The filtrate was evaporated to 100 ml, then 400 ml of methanol were added and the solid that had precipitated was suction filtered. The crude product was recrystallized once from ethyl acetate. Yield: 48.6 g (90 mmol), 90%. Purity: about 96%, according to H-NMR. The mixture of alkynes was heated under reflux for 16 hours. After cooling, the suspension was filtered through a bed of celite and the solvent was removed in vacuo. The black residue was dissolved in 1000 ml of hot ethyl acetate, the mixture was filtered hot through a bed of celite and then evaporated to about 200 ml, during which the product started to crystallize. The crystallization was completed in the refrigerator overnight, the crystals were filtered off and washed with a small amount of ethyl acetate. A second product fraction could be obtained from the mother liquor. Yield: 31.6 g (78 mmol), 78%. Purity: about 95%, according to H-NMR. 1 H-NMR.

[0491] The following compounds can be prepared analogously. Instead of ethyl acetate, toluene, n-heptane, cyclohexane or acetonitrile can also be used for recrystallization, or in the case of low solubility, for hot extraction.

[0492]

[0493]

[0494]

[0495]

[0496]

[0497]

[0498]

[0499]

[0500]

[0501] Example B186:

[0502]

[0503] were dissolved in 750 ml of toluene, 300 ml of 2-methyl-2-butene, 300 ml of water and 1.5 ml of 2 M Na2CO3solution. The mixture was heated under reflux for 16 hours. After cooling, the suspension was filtered through a bed of celite and the solvent was removed in vacuo. The black residue was dissolved in 1000 ml of hot ethyl acetate, the mixture was filtered hot through a bed of celite and then evaporated to about 200 ml, during which the product started to crystallize. The crystallization was completed in the refrigerator overnight, the crystals were filtered off and washed with a small amount of ethyl acetate. A second product fraction could be obtained from the mother liquor. Yield: 31.6 g (78 mmol), 78%. Purity: about 95%, according to H-NMR. A mixture of 42.1 g (100 mmol) of B30, 66.3 g (100 mmol) of B151, 31.8 g (300 mmol) of sodium carbonate, 580 mg (2.6 mmol) of triphenylphosphine, 200 mg (0.88 mmol) of palladium (II) acetate, 500 ml of toluene, 250 ml of ethanol and 500 ml of water was heated under reflux for 26 hours. After cooling, the solid which had precipitated out was suction filtered and washed twice with 30 ml of ethanol each time. The crude product was dissolved in 300 ml of dichloromethane and filtered through a bed of silica gel. The bed of silica gel was rinsed three times with 200 ml of dichloromethane / ethyl acetate 1:1 each time. The filtrate was washed twice with water and once with saturated sodium chloride solution and dried over sodium sulfate. The dichloromethane was stripped essentially in a rotary evaporator. During the removal of the dichloromethane in the rotary evaporator, the solid precipitated from the residual ethyl acetate, was suction filtered and washed with ethyl acetate. The crude product was recrystallized once more from ethyl acetate. Yield: 61.5 g (70 mmol), 70%. Purity: about 95%, according to HPLC. 1 H-NMR.

[0504] The following compounds can be prepared analogously.

[0505]

[0506]

[0507] Example B193:

[0508]

[0509] A mixture of 42.1 g (100 mmol) of B30, 66.3 g (100 mmol) of B151, 31.8 g (300 mmol) of sodium carbonate, 580 mg (2.6 mmol) of triphenylphosphine, 200 mg (0.88 mmol) of palladium (II) acetate, 500 ml of toluene, 250 ml of ethanol and 500 ml of water was heated under reflux for 26 hours. After cooling, the solid which had precipitated out was suction filtered and washed twice with 30 ml of ethanol each time. The crude product was dissolved in 300 ml of dichloromethane and filtered through a bed of silica gel. The bed of silica gel was rinsed three times with 200 ml of dichloromethane / ethyl acetate 1:1 each time. The filtrate was washed twice with water and once with saturated sodium chloride solution and dried over sodium sulfate. The dichloromethane was stripped essentially in a rotary evaporator. During the removal of the dichloromethane in the rotary evaporator, the solid precipitated from the residual ethyl acetate, was suction filtered and washed with ethyl acetate. The crude product was recrystallized once more from ethyl acetate. Yield: 61.5 g (70 mmol), 70%. Purity: about 95%, according to HPLC. 1 H-NMR.

[0510] Example B194:

[0511]

[0512] Analogously to the procedure of Example B193, using building block B31 instead of B30. Yield: 66%.

[0513] Example B195:

[0514]

[0515] 87.7 g (100 mmol) of B193, 25.4 g (100 mmol) of bis(pinacolyl)diborane [73183-34-3], 49.1 g (500 mmol) of potassium acetate, 2 mmol of S-Phos [657408-07-6], 1 mmol of palladium(II) acetate, 100 g of glass beads (3 mm in diameter) and 700 ml of 1,4-dioxane were added. The mixture of alkanes was heated under reflux for 16 hours. After cooling, the suspension was filtered through a diatomaceous earth bed, using 200 ml of the solution each time. The diatomaceous earth was washed three times with alkyl and the solvent was removed under vacuum. The black residue was dissolved in 1000 ml of ethyl acetate, and the mixture was filtered hot through a diatomaceous earth bed and then evaporated to about 200 ml, during which time the product began to crystallize. Crystallization was completed overnight in a refrigerator, the crystals were filtered off and washed with a small amount of ethyl acetate. A second product fraction could be obtained from the mother liquor. Yield: 72.7 g (75 mmol), 75%. Purity: approximately 97%, according to 1 H-NMR.

[0516] Example B196:

[0517]

[0518] The procedure is similar to that of Example B195. Use B194 instead of B193. Yield: 80%.

[0519] Example B197:

[0520]

[0521] A mixture of 48.5 g (50 mmol) of B195, 14.1 g (50 mmol) of 1-bromo-2-iodobenzene [583-55-1], 31.8 g (300 mmol) of sodium carbonate, 2.3 g (2 mmol) of tetrakis(triphenylphosphine)palladium(0) [14221-01-3], 500 ml of 1,2-dimethoxyethane, and 250 ml of water was heated under reflux for 60 hours. After cooling, the precipitated solid was filtered off and washed three times with 100 ml of ethanol. The crude product was dissolved in 300 ml of dichloromethane and filtered through a silica gel bed pre-slurried with dichloromethane. The silica gel was washed three times each with 200 ml of ethyl acetate. Dichloromethane was removed to 500 mbar in a rotary evaporator at a bath temperature of 50 °C. During the removal of dichloromethane in the rotary evaporator, a solid precipitated from the residual ethyl acetate was filtered off and washed with ethyl acetate. The resulting solid was recrystallized again from boiling ethyl acetate. Yield: 31.9 g (32 mmol), 64%. Purity: 95%, according to... 1 H-NMR.

[0522] Example B198:

[0523] Analogously to the procedure of Example B197. Yield: 60%.

[0524]

[0525] B: Synthesis of the ligand:

[0526] Example L1:

[0527]

[0528] A mixture of 7.9 g (14.5 mmol) of B20, 20.2 g (30.5 mmol) of B152, 63.7 g (87 mmol) of sodium carbonate, 340 mg (1.3 mmol) of triphenylphosphine, 98 mg (0.44 mmol) of palladium(II) acetate, 200 ml of toluene, 100 ml of ethanol and 200 ml of water was heated under reflux for 40 hours. After cooling, the solid that had precipitated was suction filtered and washed twice with 30 ml of ethanol each time. The crude product was dissolved in 300 ml of dichloromethane and filtered through a bed of silica gel. The bed of silica gel was rinsed three times with 200 ml of dichloromethane / ethyl acetate 1 : 1 each time. The filtrate was washed twice with water and once with a saturated sodium chloride solution and dried over sodium sulfate. The dichloromethane was essentially distilled off in a rotary evaporator. During the removal of the dichloromethane in the rotary evaporator, the solid precipitated from the residual ethyl acetate, was suction filtered and washed with ethyl acetate. Yield: 12.5 g (8.6 mmol), 59%. Purity: about 98%, according to H-NMR. 1 H-NMR.

[0529] The following compounds can be prepared analogously, wherein solvents such as ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol, DMF, DMAC or methanol can be used for recrystallization. Thermal extraction can also be carried out with these solvents or purification can be carried out by silica gel chromatography on an automated column (Torrent from Axel Semrau).

[0530]

[0531]

[0532]

[0533]

[0534]

[0535]

[0536]

[0537]

[0538]

[0539]

[0540]

[0541]

[0542]

[0543]

[0544]

[0545]

[0546]

[0547]

[0548]

[0549]

[0550]

[0551]

[0552] Example L66:

[0553]

[0554] Add 13.7g (21mmol) of B187, 4.8g (10mmol) of B8, 12.7g (60mmol) of tripotassium phosphate, 250mg (0.6mmol) of S-Phos[657408-07-6], 90mg (4mmol) of palladium(II) acetate, 100ml of toluene, and 60ml of dimethyl ether. The mixture was heated under reflux for 6 hours. After cooling, the organic phase was separated, washed twice with 50 ml of water and once with 30 ml of a saturated sodium chloride solution, dried over magnesium sulfate and filtered through a bed of diatomaceous earth pre-slurried with toluene. The bed of diatomaceous earth was rinsed with toluene. The filtrate was evaporated to dryness, then the residue was recrystallized twice from ethyl acetate. Yield: 56.5 g (4.5 mmol), 45%. Purity: about 97%, according to H-NMR. 1 H-NMR.

[0555] The following compounds can be prepared analogously, wherein solvents such as ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol, DMF, DMAC or methanol can be used for recrystallization. Thermal extraction can also be performed with these solvents, or purification can be performed by silica gel chromatography on an automated column (Torrent from Axel Semrau).

[0556]

[0557]

[0558]

[0559] C: Synthesis of metal complexes

[0560] Examples of isomer 1 -Ir2(L1 ) and isomer 2 -Ir2(L1 ) (hereinafter abbreviated as 11 -Ir2(L1 ) and 12 -Ir2(L1 )):

[0561]

[0562] A mixture of 14.5 g (10 mmol) of ligand L1, 9.8 g (20 mmol) of iridium (III) trisacetylacetonate [15635-87-7] and 100 g of hydroquinone [123-31 -9] was first introduced into a 1000 ml two-necked round-bottomed flask with a glass-coated magnetic stirrer bar. The flask was provided with a water separator (for media with a density lower than water) and an air condenser covered with argon, and was placed in a metal heating plate. The apparatus was purged from above with argon for 15 minutes via the argon cover, during which the argon stream was directed out of the side neck of the two-necked flask. A glass-coated Pt-100 thermocouple was introduced into the flask via the side neck of the two-necked flask, with the tip located directly above the magnetic stirrer bar. The apparatus was insulated by means of a few turns of loose household aluminium foil, which extended as far as the middle of the riser of the water separator. The apparatus was then rapidly heated to 250°C, measured under the Pt-100 temperature sensor, which was immersed in the molten reaction mixture stirred using a laboratory hot plate stirrer. The reaction mixture was maintained at 250°C for the next 2 hours, during which a small amount of condensate was distilled off and collected in the water separator. The reaction mixture was allowed to cool to 190°C, then 100 ml of ethylene glycol was added dropwise. The mixture was further cooled to 80°C, then 500 ml of methanol was added dropwise, and the mixture was heated under reflux for 1 hour. The suspension obtained in this way was filtered through a reversed frit, the solid was washed twice with 50 ml of methanol, then dried in vacuo. The solid obtained in this way was dissolved in 200 ml of dichloromethane and filtered through about 1 kg of silica gel (column diameter about 18 cm) pre-slurried with dichloromethane, with exclusion of air and light, with the dark components left at the start. The core fractions were cut off and evaporated in a rotary evaporator, while MeOH was added continuously dropwise for crystallization. The diastereomeric product mixture was filtered off, washed with a small amount of MeOH and dried in vacuo, then subjected to further purification.

[0563] A mixture comprising a molar ratio of 1 :1 (by 1A mixture of the ΔΔ and ΛΛ isomers (racemic) and ΛΔ isomer (meso) of the non- diastereomeric isomer metal complex of the following (H-NMR determination) was dissolved in 300 ml dichloromethane, adsorbed on 100 g of silica gel and separated by chromatography on a column of silica gel (silica gel amount: about 1.7 kg) which had been pre-slurried with toluene / ethyl acetate 95:5. The front spots were first eluted off, then the amount of ethyl acetate was gradually increased to a toluene / ethyl acetate ratio of 6:1, resulting in 7.0 g (3.8 mmol, purity 99%) of the earlier eluted isomer, hereinafter referred to as isomer 1 (11), and 7.7 g (4.2 mmol, purity 98%) of the later eluted isomer, hereinafter referred to as isomer 2 (12). Isomer 1 (11) and isomer 2 (12) were further purified from each other by hot extraction with ethyl acetate (for isomer 1) and dichloromethane (for isomer 2) four times each (in each case initially an amount of about 150 ml was introduced, extraction thimble: standard cellulose Soxhlett thimble from Whatman) under careful exclusion of air and light. Finally, the products were heated in high vacuum at 280°C. Yield: isomer 1 (11), 5.3 g red solid (2.9 mmol), 29% based on the amount of ligand used. Purity: > 99.9% according to HPLC; isomer 2 (12), 4.9 g red solid (2.7 mmol), 27% based on the amount of ligand used. Purity 99.8% according to HPLC.

[0564] The metal complexes shown below can in principle be purified by chromatography (usually using automated columns (Torrent from Axel Semrau)), recrystallization or hot extraction. Residual solvents can be removed by heating in vacuum / high vacuum, usually at 250-330°C, or by sublimation / fractionated sublimation. The yields shown for isomer 1 (11) and isomer 2 (12) always relate to the amount of ligand used.

[0565] The schemes of the complexes shown below usually show only one isomer. Isomer mixtures can be separated, but can also be used as isomer mixtures in OLED devices. There are, however, also ligand systems in which only one diastereomeric pair is formed for steric reasons.

[0566] The following compounds can be synthesized analogously. The reaction conditions are indicated by way of example for isomer 1 (11). Chromatographic separation of the diastereomeric mixtures formed is usually carried out on flash silica gel in automated columns (Torrent from Axel Semrau).

[0567]

[0568]

[0569]

[0570]

[0571]

[0572]

[0573]

[0574]

[0575]

[0576]

[0577]

[0578]

[0579]

[0580]

[0581]

[0582]

[0583]

[0584]

[0585]

[0586]

[0587]

[0588]

[0589]

[0590]

[0591]

[0592]

[0593]

[0594]

[0595]

[0596]

[0597]

[0598]

[0599] D: Functionalization of metal complexes

[0600] 1) Halogenation of iridium complexes:

[0601] A solution or suspension of 10 mmol of a complex with A x C-H groups (with A = 1-6) in the para position of iridium in 500 ml to 2000 ml of dichloromethane (DCM) depending on the solubility of the metal complex is mixed with A x 10.5 mmol of N-halosuccinimide (halogen: Cl, Br, I) at -30 to +30°C in the dark and in the absence of air and the mixture is stirred for 20 hours. Complexes with low solubility in DCM can also be reacted in other solvents (TCE, THF, DMF, chlorobenzene, etc.) and at elevated temperatures. The solvent is subsequently essentially removed in vacuo. The residue is boiled with 100 ml of methanol, the solid is suction filtered off, washed three times with 30 ml of methanol and dried in vacuo to give the halogenated iridium complex in the para position of iridium. Complexes with a HOMO (CV) of about -5.1 to -5.0 eV or less tend to oxidize (Ir(III) -> Ir(IV)) with the oxidizing agent being bromine released from NBS. This oxidation reaction is clearly seen from a distinct green discoloration or brown discoloration of the originally yellow to red solution / suspension of the complex. In these cases, a further 1-2 equivalents of NBS are added. For workup, 300-500 ml of methanol and 4 ml of hydrazine hydrate are added as reducing agent, which changes the color of the green or brown solution / suspension to yellow or red (reduction Ir(IV) -> Ir(III)). The solvent is then essentially stripped in vacuo, 300 ml of methanol are added, the solid is suction filtered off, washed three times with 100 ml of methanol each and dried in vacuo.

[0602] Substoichiometric bromination, for example monobromination and dibromination, of complexes with 3 C-H groups in the para position of iridium is usually less selective than stoichiometric bromination. These brominated crude products can be separated by chromatography (CombiFlash Torrent from A. Semrau).

[0603] Synthesis of I1-Ir2(L1-6Br):

[0604]

[0605] To a suspension of 18.3 g (10 mmol) of I1-Ir2(L1) in 2000 ml DCM was added 8.9 g (80 mmol) of N-bromosuccinimide (NBS) in one portion and the mixture was stirred for 20 hours. 4 ml of hydrazine hydrate was added followed by 300 ml MeOH. The dichloromethane was stripped essentially of in vacuo. During removal of the dichloromethane on a rotary evaporator, a red solid precipitated from the residual methanol and was suction filtered and washed with about 50 ml of methanol three times and dried in vacuo. Yield: 21.9 g (9.5 mmol), 95%; purity: >99.0% according to NMR.

[0606] The following compounds can be synthesized analogously

[0607]

[0608]

[0609]

[0610]

[0611]

[0612]

[0613]

[0614]

[0615] 2) Suzuki coupling of brominated iridium complexes

[0616] Variant A, biphasic reaction mixture:

[0617] To a suspension of 18.3 g (10 mmol) of I1-Ir2(L1) in 2000 ml DCM was added 8.9 g (80 mmol) of N-bromosuccinimide (NBS) in one portion and the mixture was stirred for 20 hours. 4 ml of hydrazine hydrate was added followed by 300 ml MeOH. The dichloromethane was stripped essentially of in vacuo. During removal of the dichloromethane on a rotary evaporator, a red solid precipitated from the residual methanol and was suction filtered and washed with about 50 ml of methanol three times and dried in vacuo. Yield: 21.9 g (9.5 mmol), 95%; purity: >99.0% according to NMR. The mixture was suspended in a mixture of alkane and 300 ml of water, and heated under reflux for 16 hours. After cooling, 500 ml of water and 200 ml of toluene were added to separate the aqueous phase. The organic phase was washed three times with 200 ml of water and once with 200 ml of saturated sodium chloride solution, and dried with magnesium sulfate. The mixture was filtered through a diatomaceous earth bed, which was then washed with toluene to almost completely remove the toluene under vacuum. 300 ml of methanol was added, and the precipitated crude product was filtered off. The product was washed three times with 50 ml of methanol each time and dried under vacuum. The crude product was then passed through an automated silica gel column (Torrent from Semrau). Subsequently, it was processed through a silica gel column such as ethyl acetate, toluene, and dimethyl ether. The complex can be further purified by thermal extraction in solvents such as alkanes, acetonitrile, cyclohexane, o-xylene or p-xylene, n-butyl acetate, etc. Alternatively, the complex can be recrystallized from these solvents and high-boiling solvents such as dimethylformamide, dimethyl sulfoxide, or mesitylene. Finally, the metal complex is heated or sublimated. The complex is then purified under high vacuum (approximately 10⁻⁶ p⁻¹). -6 Heating is carried out in millibars at a temperature range of approximately 200-300°C.

[0618] Variant B, single-phase reaction mixture:

[0619] Add 0.2 mmol of tetra(triphenylphosphine)palladium(0)[14221-01-3] to 10 mmol of bromide complex, 12-20 mmol of boric acid or borate ester (for each Br functional group), and 100-180 mmol of base (potassium fluoride, tripotassium phosphate (anhydrous or monohydrate or trihydrate), potassium carbonate, cesium carbonate, etc.) in 100-500 ml of aprotic solvent (THF, diphenylphosphine, acetone ... The mixture is placed in a suspension of alkanes, xylene, mesitylene, dimethylacetamide, NMP, DMSO, etc., and heated under reflux for 24 hours. Alternatively, other phosphines combined with Pd(OAc)2, such as triphenylphosphine, tri-tert-butylphosphine, S-Phos, X-Phos, RuPhos, XanthPhos, etc., can be used, wherein in the case of these phosphines, the preferred phosphine:palladium ratio is 3:1 to 1.2:1. The solvent is removed under vacuum, and the product is dissolved in a suitable solvent (toluene, dichloromethane, ethyl acetate, etc.) and purified as described in variant A below.

[0620] Synthesis of Ir2100:

[0621]

[0622] Variant B:

[0623] Using 23.1 g (10.0 mmol) of II-Ir(L1-6Br) and 38.0 g (120.0 mmol) of 2-(3,5-di-tert-butylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [1071924-13-4], 17.7 g (180 mmol) of potassium phosphate tribasic monohydrate, 231 mg of tetrakis(triphenylphosphine)palladium(0), 500 ml of dry dimethyl sulfoxide, reflux, 16 hours. Chromatography on silica gel with toluene / heptane twice (automated column, Torrent from Axel Semrau), followed by hot extraction with ethyl acetate / acetonitrile 1 :1 five times. Yield: 15.4 g (5.2 mmol), 52%; purity: about 99.9% according to HPLC.

[0624] The following compounds can be prepared analogously:

[0625]

[0626]

[0627]

[0628]

[0629]

[0630]

[0631]

[0632]

[0633]

[0634]

[0635]

[0636]

[0637]

[0638]

[0639]

[0640]

[0641]

[0642]

[0643] General synthetic scheme for the preparation of further metal complexes P1 to P240:

[0644]

[0645] The metal complexes described in the following tables can be prepared from the starting materials shown by the synthetic schemes described above:

[0646]

[0647]

[0648]

[0649]

[0650]

[0651]

[0652]

[0653]

[0654]

[0655]

[0656]

[0657]

[0658]

[0659]

[0660]

[0661]

[0662]

[0663]

[0664]

[0665]

[0666]

[0667]

[0668]

[0669]

[0670]

[0671]

[0672]

[0673]

[0674]

[0675]

[0676]

[0677]

[0678]

[0679]

[0680]

[0681]

[0682]

[0683]

[0684]

[0685]

[0686]

[0687]

[0688]

[0689]

[0690]

[0691]

[0692]

[0693]

[0694]

[0695]

[0696]

[0697]

[0698]

[0699]

[0700]

[0701]

[0702]

[0703]

[0704]

[0705]

[0706]

[0707]

[0708]

[0709]

[0710]

[0711]

[0712]

[0713]

[0714]

[0715]

[0716]

[0717]

[0718]

[0719]

[0720]

[0721]

[0722]

[0723]

[0724]

[0725]

[0726]

[0727] The following biphenylidene, trisphenylidene and oligophenylidene boronic acids or esters of fluorene, dibenzofuran, dibenzothiophene and carbazole can also be used in complete analogy to examples P1 to P240:

[0728] CAS: [439120-88-4], [881912-24-9], [952586-63-9], [797780-74-3], [875928-51-1], [1056044-60-0], [1268012-82-3], [1356465-28-5], [1860030-34-7], [2007912-81-2], [1343990-89-5], [1089154-61-9].

[0729] In the synthesis of ligands L1 to L76, the boronic acids or esters of examples P1 to P240 can be used and the derived metal complexes can be obtained from the resulting ligands by the methods described in relation to the synthesis of I1-Ir2(L1) and I2-Ir2(L1).

[0730] General synthetic scheme for the preparation of further metal complexes:

[0731] Starting from 2-bromo-4-R 1 - methoxypyridine, tetramethoxy substituted metal complexes, e.g. P234, are obtained in analogy to the reaction sequence shown above. These can be converted to the corresponding boronic acids or esters using pyridine hydrochloride Demehtylation in the melt at 200°C or using BBr3in dichloromethane by standard methods known in general. The tetrahydroxy complex obtained in this way can be reacted with triflic acid in the presence of a base, for example triethylamine, in dichloromethane by standard methods to give the tetra-triflate, which can be coupled with boronic acids or boronic esters by standard methods (Suzuki coupling) to give the compounds according to the application. In other transition metal promoted coupling reactions, for example Negisgi, Yamamoto, Stille, Sonogashira, Glaser, Ullmann, Grignard-Cross or Buchwald coupling, the tetra-triflate can also be functionalized with alkyl, silyl, germyl, stannyl, aryl, heteroaryl, alkoxy, amino or carbazolyl groups.

[0732]

[0733] Deuteration of the complexes:

[0734] Example P1-D25:

[0735]

[0736] A mixture of 1.95 g (1 mmol) of P1, 68 mg (1 mmol) of sodium ethoxide, 3 ml of ethanol-D1 and 50 ml of a mixture of DMSO-D6 was heated at 120°C for 8 hours. After cooling, a mixture of 0.5 ml of DCl in 5 moles of D2O and 3 ml of ethanol-D1 was added, then the solvent was removed in vacuo and the residue was chromatographed on silica gel with DCM. Yield: 1.78 g (0.9 mmol), 90%, deuteration degree > 95%.

[0737] The following compounds can be prepared analogously:

[0738]

[0739]

[0740]

[0741]

[0742]

[0743] Synthesis of the complexes by successive ortho-metalation:

[0744] 1) Successive ortho-metalation for the preparation of bimetallic complexes

[0745] The bimetallic complexes can also be obtained by consecutive orthometalation. In this method, the monometallic complex Ir(L1) or Rh(L1) can first be isolated specifically. Subsequent reaction with a further equivalent of Ir(acac)3or Rh(acac)3gives the bicyclic homo- or heterometallic complexes Ir2(L1), Rh2(L1) or Ir-Rh(L1). The bimetallic complexes are likewise formed here as a mixture of ΛΛ and ΔΔ isomers and ΔΛ and ΛΔ isomers. The ΛΛ and ΔΔ isomers form enantiomeric pairs, as do the ΔΛ and ΛΔ isomers. The diastereomeric pairs can be separated using conventional methods, for example by chromatography or fractional crystallization. Depending on the symmetry of the ligand, stereocenters can also be present simultaneously, so that meso forms are also possible. Thus, for example, in the case of orthometalation of a ligand with C 2v or C s symmetry, ΛΛ and ΔΔ isomers (racemates, C2 symmetry) and ΛΔ isomers (meso compounds, C s symmetry) are formed.

[0746] Step 1 : Monometallic complex

[0747] To prepare the monometallic complex, 25 g (11 mmol) of the ligand L1, 4.9 g (11 mmol) of tris(acetylacetonato)iridium(III) [15635-87-7] and 200 g of hydroquinone [123-31-9] were introduced into a 1000 ml two-necked round-bottomed flask with a glass-coated magnetic stirrer bar. The flask was provided with a water separator (for media with a density lower than water) and an air condenser with argon overlay and was placed in a metal heating plate. The apparatus was purged from above with argon for 15 minutes via argon overlay, during which the argon stream was directed out of the side neck of the two-necked flask. A glass-coated Pt-100 thermocouple was introduced into the flask via the side neck of the two-necked flask and the tip was positioned directly above the magnetic stirrer bar. The apparatus was then insulated by means of several loops of loose household aluminium foil, which extended as far as the middle of the riser of the water separator. The apparatus was then rapidly heated to 250°C, measured under the Pt-100 temperature sensor, which was immersed in the molten reaction mixture stirred using a laboratory hot plate stirrer. The reaction mixture was maintained at 250°C for the next 2 hours, during which a small amount of condensate was distilled off and collected in the water separator. The reaction mixture was allowed to cool to 190°C, then 100 ml of ethylene glycol was added dropwise. The mixture was further cooled to 80°C, then 500 ml of methanol was added dropwise and the mixture was heated under reflux for 1 hour. The suspension obtained in this way was filtered through a reversed glass frit and the solid was washed twice with 50 ml of methanol and then dried in vacuo. The solid obtained in this way was dissolved in 200 ml of dichloromethane and filtered through about 1 kg of silica gel (column diameter about 18 cm) which had been pre-slurried with dichloromethane, under exclusion of air and light, with the dark components being left at the start. The core fraction was cut off and evaporated in a rotary evaporator, during which MeOH was added continuously dropwise until crystallisation occurred. After suction filtration, washing with a small amount of MeOH and drying in vacuo, the monometallic complex Ir(L1) was obtained. The rhodium complex Rh(L1) can be prepared analogously starting from Rh(acac)3 [14284-92-5].

[0748] By using 1 equivalent of Ir(acac)3 or Rh(acac)3, all the ligands shown in the present application can be converted into monometallic complexes of the type Ir(L1) or Rh(L1). Only some examples are shown below.

[0749]

[0750]

[0751] The complexes Ir(L1) and Rh(L1) can now be reacted with another equivalent of Ir(acac)3or Rh(acac)3to give the bimetallic complexes I1-Ir2(L1), I2-Ir2(L1), I1-Rh2(L1), I2-Rh(L1), I1-Ir-Rh(L1) and I2-Ir-Rh(L1). It is not important which metal is introduced first.

[0752] Step 2: Dimetallic complex

[0753] To prepare the bimetallic complexes from the monometallic complexes, 24.5 g (10 mmol) of the complex Ir1(L1), 4.9 g (10 mmol) of tris(acetylacetonato)iridium(III) [15635-87-7] and 200 g of hydroquinone [123-31-9] were introduced into a 1000 ml two-necked round bottom flask with a glass-coated magnetic stir bar. The flask was equipped with a water separator (for media with a lower density than water) and an air condenser with argon overlay and placed in a metal heating plate. The apparatus was purged from above with argon for 15 minutes via argon overlay, during which time the argon stream was allowed to escape through the side neck of the two-necked flask. A glass-coated Pt-100 thermocouple was introduced into the flask via the side neck of the two-necked flask and the end was positioned directly above the magnetic stir bar. The apparatus was then insulated by means of several loops of loose household aluminum foil, where the insulation extended as far as the middle of the riser of the water separator. The apparatus was then rapidly heated to 250°C, measured under the Pt-100 temperature sensor, which was immersed in the molten reaction mixture stirred using a laboratory hot plate stirrer. The reaction mixture was maintained at 250°C for the next 2 hours, during which time a small amount of condensate was distilled off and collected in the water separator. The reaction mixture was allowed to cool to 190°C, whereupon 100 ml of ethylene glycol was added dropwise. The mixture was further cooled to 80°C, whereupon 500 ml of methanol was added dropwise and the mixture was heated under reflux for 1 hour. The suspension obtained in this way was filtered through a reversed glass frit and the solid was washed twice with 50 ml of methanol and then dried in vacuo. The solid obtained in this way was dissolved in 200 ml of dichloromethane and filtered through about 1 kg of silica gel (column diameter about 18 cm) which had been pre-slurried with dichloromethane under exclusion of air and light, where the dark components were left at the beginning. The core fraction was cut off and evaporated in a rotary evaporator, during which time MeOH was added continuously dropwise until crystallization occurred. After suction filtration, the non-diastereomeric product mixture was further purified with a small amount of MeOH and dried in vacuo.

[0754] The double metal complexes obtained by consecutive orthometalation likewise form mixtures of ΛΛ and ΔΔ isomers and ΔΛ and ΛΔ isomers. The ΛΛ and ΔΔ isomers form pairs of enantiomers, as do the ΔΛ and ΛΔ isomers. The pairs of diastereomers can be separated using conventional methods, for example by chromatography or fractional crystallization. Depending on the symmetry of the ligand, stereogenic centers can also be present simultaneously, so that meso forms are also possible. Thus, for example, in the case of orthometalation of a ligand with C 2v or C s symmetry, ΛΛ and ΔΔ isomers (racemate, C2 symmetry) and ΛΔ isomers (meso compound, C s symmetry) are formed.

[0755] All complexes of the ligands shown herein for two iridium or rhodium atoms in the present application can also be prepared by consecutive orthometalation. Likewise, heterometallic complexes of the type Ir-Rh(L) can be prepared from all the ligands shown in the present application by consecutive orthometalation.

[0756] Consecutive orthometalation can also be carried out as a one-pot reaction. For this, step 1 is first carried out to give the monometallic complex. After a reaction time of 2 hours, a further equivalent of Ir(acac)3 or Rh(acac)3 is added. After a further reaction time of 2 hours at 250°C, the mixture is worked up as described above in step 2, and the crude product obtained in this way is purified.

[0757] Only some selected examples are shown below. The diagram of the complex generally shows only one isomer. The isomer mixtures can be separated, but can also be used in OLED devices as isomer mixtures. However, there are also ligand systems in which, for steric reasons, only one pair of diastereomers is formed.

[0758]

[0759]

[0760] 2) Consecutive orthometalation for the preparation of triple metal complexes

[0761] Introduction of the first metal

[0762] Continuous orthometallation can also be used to build trimetallic complexes of the type Ir3(L52), Ir-Rh2(L52), Ir2-Rh(L52) or Rh3(L52). To this end, 22 g (10 mmol) of complex Ir1(L1), 4.9 g (10 mmol) of tris(acetylacetone)iridium(III) [15635-87-7] and 200 g of hydroquinone [123-31-9] are introduced into a 1000 ml two-necked round-bottom flask with a glass-coated magnetic stirrer bar. The flask is provided with a water separator (for media with a density lower than water) and an air condenser with argon overlay and is placed in a metal heating plate. The apparatus is purged from above with argon for 15 minutes via the argon overlay, during which the argon stream is directed out of the side neck of the two-necked flask. A glass-coated Pt-100 thermocouple is introduced into the flask via the side neck of the two-necked flask and the tip is positioned directly above the magnetic stirrer bar. The apparatus is then insulated by means of a few loops of loose household aluminum foil, where the insulation extends as far as the middle of the riser of the water separator. The apparatus is then rapidly heated to 260°C, measured under the Pt-100 temperature sensor, which is immersed in the molten reaction mixture stirred using a laboratory hot plate stirrer. The reaction mixture is maintained at 260°C for the next 2 hours, during which a small amount of condensate is distilled off and collected in the water separator. The reaction mixture is allowed to cool to 190°C, after which 100 ml of ethylene glycol is added dropwise. The mixture is further cooled to 80°C, after which 500 ml of methanol are added dropwise and the mixture is heated under reflux for 1 hour. The suspension obtained in this way is filtered through a reversed frit and the solid is washed twice with 50 ml of methanol and then dried in vacuo. The solid obtained in this way is dissolved in 400 ml of toluene and filtered through about 1 kg of silica gel (column diameter about 18 cm) which has been pre-slurried with dichloromethane under exclusion of air and light, where the dark components are left at the start. The core fraction is cut off and evaporated in a rotary evaporator, during which MeOH is added continuously dropwise until crystallization occurs. After suction filtration, washing with a small amount of MeOH and drying in vacuo, the monometallic complex Ir(L52) is obtained.

[0763] Introduction of the second metal

[0764] The complex Ir(L52) was introduced into a 1000 ml two-necked round bottom flask with a glass-coated magnetic stir bar together with 4.9 g (10 mmol) of tris(acetylacetonato)iridium(III) [15635-87-7] and 200 g hydroquinone [123-31-9]. The flask was provided with a water separator (for media with a lower density than water) and an air condenser covered with argon and placed in a metal heating plate. The apparatus was purged from above with argon for 15 minutes via the argon cover, during which the argon stream was directed out of the side neck of the two-necked flask. A glass-coated Pt-100 thermocouple was introduced into the flask via the side neck of the two-necked flask and the tip was positioned directly above the magnetic stir bar. The apparatus was then insulated by means of a few loops of loose household aluminum foil, where the insulation extended as far as the middle of the riser of the water separator. The apparatus was then rapidly heated to 260°C, measured under the Pt-100 temperature sensor, which was immersed in the molten reaction mixture stirred using a laboratory hot plate stirrer. The reaction mixture was kept at 260°C for the next 2 hours, during which a small amount of condensate was distilled off and collected in the water separator. The reaction mixture was allowed to cool to 190°C, after which 100 ml of ethylene glycol was added dropwise. The mixture was further cooled to 80°C, after which 500 ml of methanol was added dropwise and the mixture was heated under reflux for 1 hour. The suspension obtained in this way was filtered through a reversed frit and the solid was washed twice with 50 ml of methanol and then dried in vacuo. The solid obtained in this way was dissolved in 400 ml of toluene and filtered through about 1 kg of silica gel (column diameter about 18 cm) which had been pre-slurried with dichloromethane under exclusion of air and light, where the dark components were left at the start. The core fraction was cut off and evaporated in a rotary evaporator, during which MeOH was added continuously dropwise until crystallization occurred. After suction filtration, a small amount of MeOH was used for washing and drying in vacuo, obtaining the double metal complex Ir2(L52).

[0765] Introduction of the third metal

[0766] The complex Ir2(L52) is introduced into a 1000 ml two-necked round bottom flask with a glass-coated magnetic stir bar together with 4.9 g (10 mmol) of tris(acetylacetonato)iridium(III) [15635-87-7] and 200 g hydroquinone [123-31-9]. The flask is provided with a water separator (for media with a lower density than water) and an air condenser with argon overlay and is placed in a metal heating plate. The apparatus is purged from above with argon for 15 minutes via the argon overlay, during which the argon stream is directed out of the side neck of the two-necked flask. A glass-coated Pt-100 thermocouple is introduced into the flask via the side neck of the two-necked flask and the tip is positioned directly above the magnetic stir bar. The apparatus is then insulated by means of several loops of loose household aluminum foil, where the insulation extends as far as the middle of the riser of the water separator. The apparatus is then rapidly heated to 260°C, measured under the Pt-100 temperature sensor, which is immersed in the molten reaction mixture stirred using a laboratory hot plate stirrer. The reaction mixture is maintained at 260°C for the next 2 hours, during which a small amount of condensate is distilled off and collected in the water separator. The reaction mixture is allowed to cool to 190°C, after which 100 ml of ethylene glycol is added dropwise. The mixture is further cooled to 80°C, after which 500 ml of methanol is added dropwise and the mixture is heated under reflux for 1 hour. The suspension obtained in this way is filtered through a reversed glass frit and the solid is washed twice with 50 ml of methanol and then dried in vacuo. The solid obtained in this way is dissolved in 400 ml of toluene and filtered through about 1 kg of silica gel (column diameter about 18 cm) which has been pre-slurried with dichloromethane, with a dark component being left at the start. The core fraction is cut off and evaporated in a rotary evaporator, during which MeOH is added continuously dropwise until crystallization occurs. After suction filtration, a small amount of MeOH is used for washing and drying in vacuo, obtaining the trimetallic complex Ir3(L52). The trimetallic complex is further purified by hot extraction.

[0767] The trimetallic complex Ir3(L52) shown below can be prepared by successive metallation according to the reaction sequence described above or by reaction of L52 with 3 equivalents of Ir(acac)3 or Rh(acac)3.

[0768] To prepare heterotrimetallic complexes, such as Ir-Rh2(L52) or Ir2-Rh(L52), Rh(acac)3 is used instead of Ir(acac)3 in one or both steps according to the reaction sequence described above. The order of introduction of the metals is not important here.

[0769]

[0770]

[0771]

[0772]

[0773]

[0774] Example 1 : Thermal and photophysical properties and oxidation and reduction potentials

[0775] Table 1 summarizes the thermal and photochemical properties and oxidation and reduction potentials of comparative materials and selected materials according to the present application. The compounds according to the present application have improved thermal and photo stability compared to non-podal materials according to the prior art. Whereas the non-podal materials according to the prior art show brown discoloration and graying after thermal storage at 380 °C for seven days and 1 The complexes according to the present application are inert under these conditions in the range of > 2 mol% of secondary components can be detected in H-NMR. Furthermore, the compounds according to the present application have very good photo stability in anhydrous C6D6 solution under irradiation with light at a wavelength of about 455 nm. Specifically, fac-mer isomerization is not evident in H-NMR compared to non-podal complexes according to the prior art containing bidentate ligands. It is clear from Table 1 that the compounds according to the present application are all characterized by very high PL quantum efficiencies in solution. 1

[0776] Photoluminescence structure of the investigated complexes according to the present application and related comparative complexes

[0777] (the numbers in square brackets indicate the respective CAS number; the synthesis of the complexes without CAS number is described in the cited patent applications). The synthesis of Ref 15 and Ref 16 is analogous to the synthesis procedure of complexes Ref 13 and Ref 14 described in US 2003 / 0152802. Starting from the following starting materials:

[0778]

[0779] ​A mixture of 2.3 g (10 mmol) of 4,6-diphenylpyrimidine [3977-48-8] and 12.0 g (20 mmol) of iridium (acetylacetonate) bis(2-phenylpyridinato-N,C2') [945028-21-7] was suspended in 500 ml of glycerol, degassed with argon for 30 minutes and then stirred at 180 °C for 3 hours. After cooling, 1000 ml of methanol were added to the reaction mixture and the solid that had precipitated out was suction filtered. The diastereoisomers were separated by flash silica gel column chromatography on an automated column from Axel Semrau with a toluene / ethyl acetate mixture as eluent mixture. The compounds Ref 15 and Ref 16 were then further purified by hot extraction, respectively. For Ref 15, five hot extractions from ethyl acetate and for Ref 16, 3 hot extractions from n-butyl acetate. Finally, the compounds were heated under high vacuum. Yield of Ref 15: 1.2 g (1.0 mmol), 10%. Yield of Ref 16: 1.5 g (1.2 mmol), 12%. The yields are based on the amount of ligand used.

[0780]

[0781]

[0782] Ref 6 and Ref 7 form a pair of diastereoisomers, as do Ref 9 and Ref 10.

[0783] Table 1

[0784]

[0785]

[0786] * 1 Values from Inorg. Chem., 2016, 55, 1720-1727.

[0787] *2 Values from Chem. Commun, 2014, 50, 6831.

[0788] Explanation:

[0789] - Thermal stability:

[0790] Storage at 380 °C in a vacuum-sealed ampoule for 7 days. The colour change / brown discoloration / graying was evaluated visually and analyzed by H NMR spectroscopy. 1 H NMR spectroscopy.

[0791] - Photochemical stability:

[0792] A ca. 1 mM solution of anhydrous C6D6 (degassed and sealed NMR tube) was irradiated with blue light (ca. 455 nm, 1.2 W Lumispot from Dialight Corporation, USA) at room temperature.

[0793] - PLmax:

[0794] The full width at half maximum of the PL spectrum at room temperature. -5 The PL spectrum maximum of a ca. 10

[0795] - FWHM:

[0796] The full width at half maximum of the PL spectrum at room temperature.

[0797] - PLQE:

[0798] The absolute photoluminescence quantum efficiency of a ca. 10 -5 M solution in the specified solvent at room temperature, measured via an Ulbricht sphere in absolute values.

[0799] - Decay time:

[0800] The T1 lifetime was determined by time-resolved single-photon counting of a ca. 10 -5 M solution in toluene at room temperature.

[0801] - HOMO, LUMO:

[0802] Values vs. vacuum (eV) determined in dichloromethane solution (oxidized) or THF (reduced) with ferrocene as internal reference (-4.8 eV vs. vacuum).

[0803] Device examples

[0804] Example 1: Manufacture of OLEDs

[0805] The complexes according to the present application can be processed from solution. The manufacture of OLEDs based entirely on solution has been described in the literature several times, for example in WO 2004 / 037887 by spin coating. The manufacture of OLEDs based on vacuum has likewise been described several times, especially in WO 2004 / 058911. In the examples discussed below, layers applied on the basis of solution and layers applied on the basis of vacuum are combined within the OLED, so that the further processing from solution and the inclusion of the light-emitting layer and the processing in the subsequent layers (hole-blocking layer and electron-transport layer) from vacuum take place. For this purpose, the general methods described previously are adapted and combined for the cases described here (layer thicknesses, materials). The general structure is as follows: substrate / ITO (50 nm) / hole injection layer (HIL) / hole transport layer (HTL) / light-emitting layer (EML) / hole-blocking layer (HBL) / electron-transport layer (ETL) / cathode (aluminum, 100 nm). The substrates used are glass plates which have been coated with structured ITO (indium tin oxide) having a thickness of 50 nm. For better processing, these are coated with PEDOT:PSS (poly(3,4-ethylenedioxy-2,5-thiophene):polystyrene sulfonate), which is obtained from Heraeus Precious Metals GmbH & Co. KG, Germany. The PEDOT:PSS is applied by spin coating from water in air, and subsequently dried by heating at 180°C for 10 minutes in air to remove residual water. The hole transport layer and the light-emitting layer are applied to these coated glass plates. The hole transport layer used is crosslinkable. A polymer having the structure described below is used, which can be synthesized according to WO 2010 / 097155 or WO 2013 / 156130:

[0806]

[0807] The hole transport polymer is dissolved in toluene. The typical solids content of this solution is about 5 g / l, if here the typical layer thickness of 20 nm for a device is achieved by spin coating. The layer is applied by spin coating in an inert gas atmosphere (in this case argon) and dried at 180°C for 60 minutes.

[0808] The light-emitting layer always consists of at least one matrix material (host material) and a light-emitting dopant (light emitter). Furthermore, mixtures of various matrix materials and co-dopersies can be used. The expression "TMM-A (92%): Dopant (8%)" here means that material TMM-A is present in the light-emitting layer at a weight percentage of 92%, and the dopant is present in the light-emitting layer at a weight percentage of 8%. The mixture used for the light-emitting layer is dissolved in toluene or optionally chlorobenzene. The typical solid content of such a solution is about 17 g / L, and here, a typical layer thickness of 60 nm is achieved by spin coating. The layer is applied by spin coating in an inert gas atmosphere (argon in this example) and dried by heating at 150°C for 10 minutes. The materials used in this example are shown in Table 2.

[0809] Table 2: EML materials used

[0810]

[0811] The materials used for the hole blocking layer and electron transport layer are applied in a vacuum chamber via thermal vapor deposition. The electron transport layer here can, for example, consist of more than one material, which are mixed with each other in a specific volume ratio through co-evaporation. Expressions such as ETM1:ETM2 (50%:50%) indicate that materials ETM1 and ETM2 are present in the layer at a 50% volume ratio, respectively. The materials used in this example are shown in Table 3.

[0812] Table 3: HBL and ETL Materials Used

[0813]

[0814] The cathode was formed by thermal evaporation of a 100 nm aluminum layer. The OLED was characterized using standard methods. For this purpose, the electroluminescence spectrum was determined, assuming the current / voltage / luminous density characteristic line (IUL characteristic line) of the Lambertian emission characteristics, and the (operating) lifetime was determined. The IUL characteristic line was used to determine characteristic values, such as operating voltage (V) and efficiency (cd / A) at a specific brightness. At 1000 cd / m²... 2 Electroluminescence spectra were measured at luminous density, and CIE 1931 x and y color coordinates were calculated accordingly. The EML mixtures and structures of the studied OLED components are shown in Tables 4 and 5. Related results are available in Table 6.

[0815] Table 4: EML mixtures of the studied OLED components

[0816]

[0817]

[0818] Table 5: Structure of the OLED assemblies investigated

[0819]

[0820]

[0821] Table 6: Results of solution-processed OLEDs (at 1000 cd / m 2 of luminance)

[0822] Examples EQE [%] CIE x CIE y At 60 mA / cm 2 Under LT90 V1 16.2 0.66 0.34 276 V2 15.7 0.67 0.33 123 V3 18.2 0.64 0.36 298 E-1 20.0 0.65 0.35 359 E-2 19.9 0.66 0.34 317 E-3 18.6 0.66 0.34 315 E-4 18.6 0.64 0.35 304 E-5 20.1 0.63 0.37 277 E-6 19.8 0.68 0.32 221 E-7 18.7 0.68 0.32 298 E-8 19.7 0.63 0.37 248 E-9 18.4 0.67 0.33 199 V4 15.0 0.68 0.33 70 V5 8.6 0.65 0.35 34 E-10 19.1 0.67 0.33 171 E-11 18.9 0.67 0.33 165 E-12 18.8 0.67 0.33 154 E-13 16.7 0.65 0.35 93 E-14 18.5 0.55 0.45 137 E-15 19.4 0.65 0.35 133 E-16 18.8 0.68 0.32 85 E-17 19.8 0.65 0.35 348 E18 10.2 0.71 0.28 112 E-19 14.8 0.55 0.44 84 E-20 18.2 0.68 0.32 16 E-21 18.0 0.70 0.31 92 E-22 13.3 0.65 0.35 111 E-23 21.6 0.68 0.32 569 E-24 24.6 0.68 0.32 493 E-25 23.6 0.68 0.32 93 E-26 23.8 0.68 0.32 236

[0823] All compounds P1 to P234 shown above and the deuterated compounds shown above can be used analogously and lead to comparable results.

[0824] As an alternative to the fabrication by spin coating, the solution-processed layers can also be fabricated by inkjet printing, inter alia. In the examples discussed below, the layers applied on the basis of solution and the layers applied on the basis of vacuum are combined again within the OLED, so that the further processing from solution and the inclusion of the light-emitting layer and the processing in the subsequent layers (hole-blocking layer and electron-transport layer) from vacuum. Furthermore, the general structure is as follows: substrate / ITO (50 nm) / hole-injection layer (HIL) / hole-transport layer (HTL) / light-emitting layer (EML) / hole-blocking layer (HBL) / electron-transport layer (ETL) / cathode (aluminum, 100 nm). The substrates used are glass plates which have been coated with structured ITO (indium tin oxide) having a thickness of 50 nm and a pixelated bank material.

[0825] The hole-injection layer was printed onto the substrate, dried in vacuum and subsequently heated in air at 180°C for 30 minutes. The hole-transport layer was printed onto the hole-injection layer, dried in vacuum and then heated in the glovebox at 230°C for 30 minutes. Subsequently, the light-emitting layer was printed, dried in vacuum and heated in the glovebox at 160°C for 10 minutes. All printing steps were carried out in air under yellow light.

[0826] The hole-injection material used was a composition according to PCT / EP2015 / 002476 comprising a polymer (e.g. polymer P2) and a salt (e.g. salt D1). This was dissolved in 3-phenoxytoluene and diethyleneglycol butylmethyl ether in a ratio of 7:3. The hole-transport material was processed from the same solvent mixture. The light-emitting layer was printed from pure 3-phenoxytoluene.

[0827] The EML mixtures and structures of the OLED assemblies investigated are shown in Tables 7 and 8. The relevant results can be found in Table 9. Good pixel uniformity was achieved.

[0828] Table 7: EML mixtures of the OLED assemblies investigated

[0829]

[0830] Table 8: Structure of the OLED assemblies investigated

[0831] Examples HIL (thickness) HTL (thickness) EML thickness HBL (thickness) ETL (thickness) E-28 HIL (60 nm) HTL2 (20 nm) 60 nm ETM-1 (10 nm) ETM-1 (50%): ETM-2 (50%) (40 nm) E-29 HIL (60 nm) HTL2 (20 nm) 60 nm ETM-1 (10 nm) ETM-1 (50%): ETM-2 (50%) (40 nm) E-30 HIL (60 nm) HTL2 (20 nm) 60 nm ETM-1 (10 nm) ETM-1 (50%): ETM-2 (50%) (40 nm)

[0832] Table 9: Results of solution-processed OLEDs (at 1000 cd / m 2 measured at a luminance of 1000 cd / m2)

[0833] Examples EQE [%] CIE x CIE y At 60 mA / cm 2 Under LT90 E-28 21.0 0.66 0.34 503 E-29 19.4 0.67 0.33 64 E-30 20.8 0.68 0.32 156 BRIEF DESCRIPTION OF DRAWINGS

[0834] Figure 1 : Single crystal structure of compound Ir2(L1)

[0835] ORTEP representation with 50% probability level)

[0836] a) Side view of the ligand bridging the iridium centers.

[0837] b) Top view of the ligand bridging the iridium centers.

[0838] For better clarity, hydrogen atoms are not shown.

[0839] Figure 2 : Single crystal structure of compound Ir2100

[0840] ORTEP representation with 50% probability level)

[0841] a) Side view of the ligand bridging the iridium centers.

[0842] b) Top view of the ligand bridging the iridium centers.

[0843] For better clarity, hydrogen atoms are not shown.

[0844] Figure 3 : Single crystal structure of compound Ir2(L75)

[0845] ORTEP representation with 50% probability level)

[0846] a) Side view of the ligand bridging the iridium centers.

[0847] b) Top view of the ligand bridging the iridium centers.

[0848] For better clarity, hydrogen atoms are not shown.

Claims

1. A compound of formula (1a) or formula (2a), The following applies to the symbols and markings used: M is iridium; In formula (1a), Q represents a group of one of formulas (Q-1) to (Q-3), and in formula (2a), Q for p = 0 represents a group of one of formulas (Q-4) to (Q-9), or for p = 1 represents a group of formulas (Q-16) to (Q-19). The dashed bond in each case indicates the connection in formula (1a) or (2a), and * marks the position where the group is coordinated with M; D is either C or N in each occurrence, and the group R, which is clearly drawn in the adjacent position of D, is selected from H, D, CH3 and CD3 in each occurrence, either in the same or different cases. X is C; p is 0 or 1; V is a group of formula (6a'''), One of the dashed bonds represents a bond connected to the corresponding 6-membered aryl or heteroaryl cyclic group depicted in formula (1a) or (2a), and the other two dashed bonds each represent a bond connected to a portion of the ligand L. L is, in each occurrence, either identically or differently, a bidentate monoanion partial ligand, wherein the partial ligand is, in each occurrence, either identically or differently, selected from the structures of formulas (L-1-1a) and (L-2-1a). The symbols used have the meanings given above, and "o" indicates the bond position with group V; R is, in each occurrence, either the same or different, H, D, a straight-chain alkyl group having 1 to 6 carbon atoms, or a phenyl group, wherein in each case the phenyl group may be one or more of the R groups. 1 replace; R 1 Each time it appears, it is either the same or different H, D, a straight-chain alkyl group having 1 to 5 C atoms, or a branched alkyl group having 3 to 5 C atoms.

2. The compound according to claim 1, characterized in that, For p = 0, all four partial ligands L are identical and are substituted in the same way, or for p = 1, all six partial ligands L are identical and are substituted in the same way.

3. A method for preparing the compound according to any one of claims 1 to 2, said method being carried out by reacting a free ligand with a metal alkoxide of formula (58), a metal diketide of formula (59), a metal halide of formula (60), or a metal carboxylate of formula (61), or by reacting with an iridium or rhodium compound having an alcohol anion and / or a halide anion and / or a hydroxyl group and a diketide anion group. Wherein M and R have the meanings shown in claim 1, Hal = F, Cl, Br or I, and the iridium and rhodium raw materials may also be in the form of the corresponding hydrates.

4. A mixture comprising at least one compound according to any one of claims 1 to 2 and at least one other compound.

5. A formulation comprising at least one compound according to any one of claims 1 to 2 or at least one mixture according to claim 4 and at least one solvent.

6. Use of a compound according to any one of claims 1 to 2 or a mixture according to claim 4 in an electronic device.

7. An electronic device comprising at least one compound according to any one of claims 1 to 2.

8. The electronic device according to claim 7, wherein the electronic device is an organic electroluminescent device, characterized in that... The compound according to any one of claims 1 to 2 is used as the luminescent compound in one or more luminescent layers.

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