Metal complexes for use as emitters in organic electroluminescent devices

Abstract

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

Description

[0001] This application is a divisional application of Chinese Patent Application No. 201780046022.3 (corresponding international application number PCT / EP2017 / 068292), which was filed on July 25, 2016, entitled “Metal complexes used as light emitters in organic electroluminescent devices”. Technical Field

[0002] This invention relates to metal complexes, which are substituted with aromatic and bicyclic aliphatic substituents, and are suitable as light emitters in organic electroluminescent devices. Background Technology

[0003] According to existing technology, triplet emitters used in phosphorescent organic light-emitting devices (OLEDs) are particularly ortho-metallized iridium or platinum complexes with aromatic ligands, wherein the ligands are bonded to the metal via a negatively charged carbon atom and an uncharged nitrogen atom or via a negatively charged carbon atom and an uncharged carbene carbon atom. Examples of these complexes are tris(phenylpyridyl)iridium(III) and its derivatives, wherein the ligands used are, for example, 1-phenylisoquinoline or 3-phenylisoquinoline, 2-phenylquinoline or phenyl carbene.

[0004] The problem addressed by this invention is to provide novel metal complexes suitable for use as light emitters in OLEDs. A specific objective is to provide light emitters exhibiting directional emission and / or improved properties in terms of efficiency, operating voltage, and / or lifetime. Directional emission allows for higher quantum efficiency by increasing the coupling output of light from the component, resulting in higher overall efficiency for the OLED. Consequently, the component can be driven with lower current, leading to a longer lifetime as another advantage.

[0005] It has been discovered that the aforementioned problems are unexpectedly solved by iridium or platinum complexes containing one or more substituents from aromatic and heteroaromatic groups, as well as aliphatic bicyclic and oligocyclic groups, and are highly suitable for use in organic electroluminescent devices. This invention provides these complexes and organic electroluminescent devices comprising them. Summary of the Invention

[0006] This invention provides a compound of formula (1):

[0007]

[0008] The symbols and markings used are as follows:

[0009] M is the same or different in each case, and is an organometallic iridium complex or an organometallic platinum complex;

[0010] Ar is the same or different in each case, and is a linearly bonded arylene or heteroarylene having 6 to 30 aromatic ring atoms and may be substituted by one or more R groups;

[0011] B is a group of formula (2) below:

[0012]

[0013] The dashed bond indicates that the group is associated with Ar or R. B The connection, and in addition:

[0014] Y 1 Y 2 Y 3 In each case, it may be the same or different, and is a CR2, CR2-CR2, CR2-CR2-CR2, CR2-CR2-CR2-CR2, CR=CR, or ortho-bonded phenylene group, which may be substituted by one or more R groups; meanwhile, Y 1 Y 2 and / or Y 3 Groups can be linked together by single bonds or via R groups to form oligocyclic ring groups;

[0015] R B In each case, the alkyl group may be the same or different, and is selected from M or H, D, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group in each case may be one or more R 1 Group substitution, or an aromatic ring system or heteroaromatic ring system having 5 to 40 aromatic ring atoms and in each case being substituted with one or more R groups. 1 Group substitution;

[0016] R is the same or different in each case, and is 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)(R 1 )2, S(=O)R 1 S(=O)2R 1 OSO2R 1A straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group in each case may be one or more R 1 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 1 C = CR 1 C≡C, Si(R) 1 2. C=O, NR 1 O, S or CONR 1 Replacement, or an aromatic ring system or heteroaromatic ring system having 5 to 40 aromatic ring atoms and in each case can be replaced by one or more R 1 Group substitution; at the same time, two R groups can also form a ring system together;

[0017] R 1 In each case, they are either the same or different, and are 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 A straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group in each case may be one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 2 C = CR 2 C≡C, Si(R) 2 2. C=O, NR 2 O, S or CONR 2 Replacement, or an aromatic ring system or heteroaromatic ring system having 5 to 40 aromatic ring atoms and in each case can be replaced by one or more R 2 Group substitution; simultaneously, two or more R groups 1 Groups can form ring systems together;

[0018] R 2 In each case, it may be the same or different, and is H, D, F, or an aliphatic, aromatic or heteroaromatic organic group having 1 to 20 carbon atoms, especially a hydrocarbon group, in which one or more hydrogen atoms may also be replaced by F;

[0019] n is 1, 2, 3, 4, 5, or 6;

[0020] p is the same or different in each case, and is between 1 and 100;

[0021] q is the same or different in each case, and is between 0 and 100;

[0022] m is the same or different in each case, and is between 1 and 100.

[0023] p, q, and m are integers.

[0024] When q = 0, the compound is a compound of formula (1A), and when q = 1 to 100, it is a compound of formula (1B):

[0025]

[0026] The symbols and markings used herein have the definitions given above.

[0027] Preferably, p is the same or different in each case, and is 1 to 50, more preferably 1 to 20, even more preferably 1 to 10, and particularly 1, 2, 3, or 4. Furthermore, preferably, q is the same or different in each case, and is 0 to 50, more preferably 0 to 10, even more preferably 0 to 10, and particularly 0, 1, 2, 3, or 4. Preferably, n is the same or different in each case, and is 1 to 50, more preferably 1 to 20, even more preferably 1 to 10, and particularly 1, 2, 3, 4, or 5. More specifically, the preferred embodiments of p and m listed herein apply simultaneously.

[0028] Furthermore, it is preferred that n = 1, 2 or 3, more preferably n = 1 or 2, and even more preferably n = 1.

[0029] When two R or R 1 When groups together form a ring system, it can be monocyclic or polycyclic, and aliphatic, heteroaliphatic, aromatic, or heteroaromatic. In this case, the groups forming the ring system together can be adjacent, meaning that these groups are bonded to the same carbon atom or to carbon atoms directly bonded to each other, or they can be removed from each other.

[0030] The phrase "two or more groups may form a ring together" should be understood in the context of this specification to specifically mean that two groups are connected to each other by chemical bonds, thereby formally eliminating two hydrogen atoms. This is illustrated by the following scheme:

[0031]

[0032] Ring formation of bicyclic, tricyclic, and oligocyclic structures is also feasible. However, the above wording should also be understood to mean that if one of the two groups is hydrogen, then the second group binds to the position bonded to the hydrogen atom, thereby forming a ring. This should be illustrated by the following scheme:

[0033]

[0034] In a very similar way, this should also be understood to mean that if both groups are hydrogen atoms, then ring formation occurs via a single bond rather than two hydrogen atoms.

[0035] The formation of aromatic ring systems should be explained through the following scheme:

[0036]

[0037] Such ring formation is feasible in groups bonded to carbon atoms directly bonded to each other or in groups bonded to further removed carbon atoms. Preferably, such ring formation occurs in groups bonded to carbon atoms directly bonded to each other or to the same carbon atom.

[0038] In the context of this invention, an aryl group contains 6 to 40 carbon atoms; in the context of this invention, a heteroaryl group contains 2 to 40 carbon atoms and at least one heteroatom, provided that the total number of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O, and / or S. Aryl or heteroaryl is hereby understood to mean a simple aromatic ring, i.e., benzene; or a simple heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc.; or a fused aryl or heteroaryl group, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. Furthermore, in the context of this invention, an aryl should be understood to mean a group in which two, three, or more phenyl groups directly bonded to each other are bridged by a CR2 group, i.e., for example, fluorenyl, spirodifluorenyl, or inden[2]fluorenyl.

[0039] In the context of this invention, an aromatic ring system contains 6 to 40 carbon atoms. In the context of this invention, a heteroaromatic ring system contains 1 to 40 carbon atoms and at least one heteroatom, provided that the total number of carbon atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O, and / or S. In the context of this invention, an aromatic ring system or a heteroaromatic ring system should be understood to mean a system that does not necessarily contain only aryl or heteroaryl groups, but in which two or more aryl or heteroaryl groups may also be interrupted by non-aromatic units (preferably less than 10% of non-H atoms), such as carbon atoms, nitrogen atoms, oxygen atoms, or carbonyl groups. For example, in the context of this invention, systems such as triarylamines, diaryl ethers, stilbenesnes, etc., should therefore also be considered aromatic ring systems, and similarly, systems in which two or more aryl groups are interrupted by, for example, straight-chain or cyclic alkyl or silyl groups are also considered aromatic ring systems. Furthermore, systems in which two or more aryl or heteroaryl groups are directly bonded to each other, such as biphenyl, terphenyl, tetraphenyl, or bipyridine, should also be considered as aromatic or heteroaromatic ring systems.

[0040] In the context of this invention, cyclic alkyl, alkoxy, or thioalkoxy are understood to mean monocyclic, bicyclic, or polycyclic groups.

[0041] In the context of this invention, the C1 to C20 alkyl groups, wherein individual hydrogen atoms or CH2 groups may be replaced by the aforementioned groups, are understood to mean, for example, 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-methyl Cyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1-yl, 1 1-Dimethyl-n-hept-1-yl, 1,1-Dimethyl-n-oct-1-yl, 1,1-Dimethyl-n-dec-1-yl, 1,1-Dimethyl-n-dodecane-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-hexane-1-yl, 1,1-Diethyl-n-heptane-1-yl, 1,1-Diethyl-n-octane-1-yl The groups are: 1,1-diethyl-n-decyl-1-yl, 1,1-diethyl-n-dodecyl-1-yl, 1,1-diethyl-n-tetradecyl-1-yl, 1,1-diethyl-n-hexadecyl-1-yl, 1,1-diethyl-n-octadecyl-1-yl, 1-(n-propyl)cyclohexyl-1-yl, 1-(n-butyl)cyclohexyl-1-yl, 1-(n-hexyl)cyclohexyl-1-yl, and 1-(n-octyl)cyclohexyl-1-yl. Alkenyl is understood to mean, for example, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, or cyclooctadienyl. Alkynyl is understood to mean, for example, ethynyl, propynyl, butynyl, penynyl, hexynyl, heptenyl, or octynyl. C1 to C 20 Alkoxy is understood to mean, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, or 2-methylbutoxy.

[0042] Aromatic or heteroaromatic ring systems having 5-40 aromatic ring atoms, and in each case potentially substituted by the aforementioned groups, and capable of being linked to aromatic or heteroaromatic systems via any desired position, are understood to mean, for example, derived from the following groups: benzene, naphthalene, anthracene, benzo[a]anthracene, phenanthrene, benzo[a]phenanthrene, pyrene, etc. Perylene, fluoranthene, benzo[a]fluoranthene, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, diphenylenex, terphenyl, ditriphenylenex, fluorene, spirodifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-indeno[a]fluorene or trans-indeno[a]fluorene, cis-monobenzo[a]fluorene or trans-monobenzo[a]fluorene, cis-dibenzo[a]fluorene or trans-dibenzo[a]fluorene, trimer indene, isotrimer indene, spirotrimer indene, spiro[a]fluorene Isotrimeric indene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indole-carbazole, indene-carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenanthrene Azides, pyrazoles, indazoles, imidazoles, benzimidazoles, naphthiazoles, phenanthreneimidazoles, pyridinium imidazoles, pyrazinium imidazoles, quinoxaline imidazoles azole, benzo[ azole, naphtho azole, anthraquinone azole, phenanthrene azole, isotonic Azole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazathane, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenazine Azides, phenothiazines, fluorescent rings, naphthidine, azacarbazole, benzo[a]carbline, phenanthroline, 1,2,3-triazoles, 1,2,4-triazoles, benzo[a]triazoles, 1,2,3- diazole, 1,2,4- diazole, 1,2,5- diazole, 1,3,4- Diazoles, 1,2,3-thiadiazoles, 1,2,4-thiadiazoles, 1,2,5-thiadiazoles, 1,3,4-thiadiazoles, 1,3,5-triazines, 1,2,4-triazines, 1,2,3-triazines, tetrazolium, 1,2,4,5-tetraazines, 1,2,3,4-tetraazines, 1,2,3,5-tetraazines, purines, pteridines, indazines, and benzothiadiazoles.

[0043] In a preferred embodiment of the invention, the triplet energy of fragment M is higher than that of fragment -[[Ar]]. p -B-[Ar] q ] m -R B The triplet energy does not exceed 0.1 eV. This fragment corresponds to -[[Ar]] at q = 0. p -B] m -R B Or, when q = 1 to 100, it corresponds to -[[Ar]].p -B-[Ar] p ] m -R B More preferably, the triplet energy of fragment M is equal to or less than that of fragment -[[Ar]] p -B-[Ar]q] m -R B The triplet energy is preferably at least 0.1 eV lower.

[0044] In the context of this invention, the triplet energy of fragment M is understood to mean having a structure of M, but in each case having a hydrogen atom and not having -[[Ar]]. p -B-[Ar] q ] m -R B Triplete energy of compounds with substituents. (Fragment - [Ar]) p -B-[Ar] q ] m -R B The triplet energy is understood to refer to a structure with H-[[Ar]] p -B-[Ar] q ] m -R B The triplet state energy of the compound. This triplet state energy was determined by quantum chemical calculations, as described in the General Terms section below.

[0045] Preferred iridium or platinum complexes M are described below. As mentioned above, these are organometallic complexes. In the context of this invention, an organometallic complex is a complex having at least one metal-carbon bond.

[0046] In a preferred embodiment of the invention, the iridium or platinum complex is uncharged, i.e., electrically neutral. The iridium complex preferably contains three bidentate monoanion ligands or one tridentate hexadentate trianion ligand, and the platinum complex contains two bidentate monoanion ligands or one tetradentate dianion ligand.

[0047] The bond between the ligand and iridium can be a coordinate bond or a covalent bond, or the covalent fraction of the bond can vary depending on the ligand. When referring to the coordination or binding of a ligand or subligand with iridium in this application, it means, in the context of this application, any kind of bond between the ligand or subligand and iridium, regardless of the covalent fraction of the bond.

[0048] In a preferred embodiment of the invention, M is an iridium complex. More preferably, it is an iridium complex having a tripentate hexadentate ligand, as described below. In this case, the tripentate hexadentate ligand contains three bidentate subligands, which may be the same or different and coordinated with an iridium atom, wherein the three bidentate subligands are connected via a bridging group of formula (3) or formula (4).

[0049]

[0050] The dashed bond represents the bond between the bidentate subligand and this structure, R, R 1 and R 2 It has the definition given above, and in addition:

[0051] X 1 It may be the same or different in each case, and it is CR or N;

[0052] A 1 It is the same or different in each case, and is C(R)2 or O;

[0053] A 2 It is the same or different in each case, and is CR, P (=O), B or SiR, provided that when A 2 When =P (=O), B, or SiR, the symbol A 1 It is O and with that A 2 The bond symbol A is neither -C(=O)-NR'- nor -C(=O)-O-;

[0054] A is the same or different in each case, and is a group of -CR=CR-, -C(=O)-NR'-, -C(=O)-O-, -CR2-CR2- or the following formula (5):

[0055]

[0056] The dashed line indicates the position of the bond between the bidentate subligand and the structure, and * indicates the connection position between the unit of formula (5) and the central cyclic group (i.e. the group explicitly included in formula (3) or formula (4)).

[0057] X 2 In each case, they are either the same or different, and are CR or N, or two adjacent X. 2 The groups together are NR, O, or S, thus forming a five-membered ring, and the remaining X 2 In each case, it is the same or different, and it is CR or N; or when X in the ring 3 When one of the groups is N, two adjacent X 2The groups together are either CR or N, thus forming a five-membered ring; the prerequisite is that there are no more than two adjacent X groups. 2 The group is N;

[0058] X 3 In each case it is C, or an X. 3 The group is N and another X in the same ring 3 The group is C; the prerequisite is that X in the ring 3 When one of the groups is N, two adjacent X 2 The groups together are CR or N;

[0059] R' may be the same or different in each case, and is H, D, a straight-chain alkyl group having 1 to 20 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl group may be one or more R's in each case. 1 Group substitution, and one or more non-adjacent CH2 groups can be replaced by Si(R) 1 )2 substitution, or an aromatic ring system or a heteroaromatic ring system, wherein the aromatic ring system or heteroaromatic ring system has 5 to 40 aromatic ring atoms and in each case can be replaced by one or more R 1 Group substitution;

[0060] In addition to the bridging group of formula (3) or formula (4), the three bidentate subligands can also be circumscribed by another bridging group to form a cavitary compound.

[0061] -[[Ar] p -B-[Ar] q ] m -R B The group can be attached to the complex M at the group of formula (3) or formula (4) or at one of the subligands.

[0062] The structure of a hexadentate tripopod ligand can be schematically represented by the following formula (Lig):

[0063]

[0064] Wherein V represents the bridging group of formula (3) or formula (4), and L1, L2, and L3 are the same or different in each case, and each is a bidentate subligand, preferably a monoanionic bidentate subligand. “Bbident” means that a specific subligand in the complex M is coordinated or bound to iridium via two coordination sites. “Triped” means that the ligand has three subligands bonded to the bridging group V or the bridging group of formula (3) or formula (4). Since the ligand has three bidentate subligands, the overall result is a hexadecanter, that is, a ligand coordinated or bound to iridium via six coordination sites. In the context of this application, the term “bidentate subligand” means that if the bridging group of formula (3) or formula (4) is not present, then the unit would be a bidentate ligand. However, since it formally deprives the hydrogen atom in the bidentate ligand and is connected to the bridging group of formula (3) or formula (4), it is not a standalone ligand, but part of the resulting hexadentate ligand, and therefore the term "subligand" is used for it.

[0065] The iridium complex M formed with the ligand of this formula (Lig) can therefore be schematically represented by the following formula:

[0066]

[0067] Where V represents the bridging base of formula (3) or formula (4), and L1, L2 and L3 are the same or different in each case, and each is a bidentate subligand.

[0068] The following describes preferred embodiments of the bridging group of formula (3) or formula (4) connecting three bidentate subligands. Suitable embodiments of the group of formula (3) are structures of formulas (6) to (9), and suitable embodiments of the group of formula (4) are structures of formulas (10) to (14):

[0069]

[0070] The symbols have the definitions given above.

[0071] The preferred R groups in formulas (6) to (14) are as follows:

[0072] R is the same or different in each case, and is H, D, F, CN, OR 1 A straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of which can be substituted by one or more R 1 Group substitution, or an aromatic ring system or heteroaromatic ring system having 5 to 24 aromatic ring atoms and in each case being substituted by one or more R groups. 1 Group substitution;

[0073] R1 It is the same or different in each case, and is H, D, F, CN, OR 2 A straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of which can be substituted by one or more R 2 Group substitution, or an aromatic ring system or heteroaromatic ring system having 5 to 24 aromatic ring atoms and in each case being substituted by one or more R groups. 2 Group substitution; simultaneously, two or more adjacent R groups... 1 Groups can form ring systems together;

[0074] R 2 In each case, it may be the same or different, and is H, D, F, or an aliphatic, aromatic, and / or heteroaromatic organic group having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may also be replaced by F.

[0075] The R groups particularly preferred in formulas (6) to (14) are as follows:

[0076] R can be the same or different in each case, and is H, D, F, CN, a straight-chain alkyl group having 1 to 4 carbon atoms or a branched or cyclic alkyl group having 3 to 6 carbon atoms, each of which can be represented by one or more R. 1 Group substitution, or an aromatic ring system or heteroaromatic ring system having 6 to 12 aromatic ring atoms and in each case being substituted by one or more R groups. 1 Group substitution;

[0077] R 1 In each case, it may be the same or different, and is H, D, F, CN, a straight-chain alkyl group having 1 to 4 carbon atoms or a branched or cyclic alkyl group having 3 to 6 carbon atoms, each of which may be substituted by one or more R 2 Group substitution, or an aromatic ring system or heteroaromatic ring system having 6 to 12 aromatic ring atoms and in each case being substituted by one or more R groups. 2 Group substitution; simultaneously, two or more adjacent R groups... 1 Groups can form ring systems together;

[0078] R 2 In each case, it may be the same or different, and it is H, D, F, or an aliphatic or aromatic hydrocarbon group having 1 to 12 carbon atoms.

[0079] In a preferred embodiment of the invention, all X1 groups in formula (3) are CR, and therefore, the central trivalent ring of formula (3) is benzene. More preferably, all X 1 All groups are CH. In another preferred embodiment of the invention, all X 1 All groups are nitrogen atoms, and therefore, the central trivalent ring of formula (3) is a triazine. The preferred embodiment of formula (3) is therefore the structure of formulas (6) and (7) described above. More preferably, the structure of formula (6) is the structure of formula (6'):

[0080]

[0081] The symbols have the definitions given above.

[0082] In another preferred embodiment of the invention, all A groups in formula (4) 2 All groups are CR. More preferably, all A groups are CR. 2 All groups are CH. The preferred embodiment of formula (4) is therefore the structure of formula (10) described above. More preferably, the structure of formula (10) is the structure of formula (10') or formula (10"):

[0083]

[0084] The symbols have the definitions given above, and R is preferably H. Groups of formula (10') are particularly preferred here.

[0085] When A 2 When it is CR, especially when all A 2 When both are CR, it is especially important when A is also present. 1 When A has 0, 1, 2, or 3 of them, especially when 3 are CR2, 2 The R groups can be positioned differently depending on the configuration. Small R groups, such as H or D, are preferred. Preferably, they are all pointing away from the metal (apex) or all pointing inwards towards the metal (intercalation). This is illustrated below by examples of complexes with ester-bridged groups. The same applies to o-aryl bridged groups, o-heteroaryl bridged groups, 1,2-olefin bridged groups, imine bridged groups, and amide bridged groups, regardless of how the bridged group is oriented, i.e., whether the carbonyl group of the ester / amide bridged group or the nitrogen atom of the imine bridged group is bonded to the cyclohexane ring or to an aromatic system with a bidentate subligand.

[0086]

[0087] For clarity, the third subligand is not shown but indicated only by a dashed bond. Therefore, it is preferred to use complexes in which at least one of these two configurations can be employed. These are complexes in which all three A groups are arranged in a planar manner on the central ring.

[0088] Preferred A groups present in the structures of formulas (3) and (4) and formulas (6) through (14) are described below. The A group can be the same or different in each case, and can be an alkenyl, amide, ester, or ortho-bonded arylene or heteroarylene of formula (5). When A is alkenyl, it is a cis-bonded alkenyl. In the case of asymmetric A groups, any orientation of the group is possible. This is illustrated below by the example of A = -C(=O)-O-. This results in the following possible orientations of A, all of which are covered by this invention:

[0089]

[0090] In a preferred embodiment of the invention, A is the same or different in each case, more preferably the same, and selected from -C(=O)-O-, -C(=O)-NR'-, and groups of formula (5). More preferably, two A groups are the same and have the same substitutions, and the third A group is different from the first two A groups, or all three A groups are the same and have the same substitutions. The preferred combination of the three A groups in formulas (3) and (4) and in the preferred embodiments is:

[0091] Equation (5) Equation (5) Equation (5) -C(=O)-O- -C(=O)-O- -C(=O)-O- -C(=O)-O- -C(=O)-O- Equation (5) -C(=O)-O- Equation (5) Equation (5) -C(=O)-NR'- -C(=O)-NR'- -C(=O)-NR'- -C(=O)-NR'- -C(=O)-NR'- Equation (5) -C(=O)-NR'- Equation (5) Equation (5)

[0092] Here, it is particularly preferred that all three A symbols are each a group of formula (5).

[0093] When A is -C(=O)-NR'-, R' is preferably the same or different in each case, and is a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or an aromatic ring system or heteroaromatic ring system having 6 to 24 aromatic ring atoms and in each case can be one or more R's. 1 Group substitution. More preferably, R' is the same or different in each case, and is a straight-chain alkyl group having 1 to 5 carbon atoms or a branched or cyclic alkyl group having 3 to 6 carbon atoms, or an aromatic ring system or heteroaromatic ring system having 6 to 12 aromatic ring atoms and in each case can be substituted by one or more R groups. 1 The groups are substituted, but preferably unsubstituted.

[0094] Preferred embodiments of the group of formula (5) are described below. The group of formula (5) may represent a heteroaromatic five-membered ring or an aromatic or heteroaromatic six-membered ring. In a preferred embodiment of the invention, the group of formula (5) contains no more than two heteroatoms in the aromatic or heteroaromatic unit, more preferably no more than one heteroatom. This does not mean that any substituent bonded to the group cannot contain heteroatoms. Furthermore, this definition does not mean that the ring formed by the substituent cannot produce a fused aromatic or heteroaromatic structure, such as naphthalene, benzimidazole, etc.

[0095] When the two X in equation (5) 3 When all groups are carbon atoms, the preferred embodiment of the group in formula (5) is the structure of formulas (15) to (31), and when an X 3 The group is a carbon atom and another X in the same ring. 3 When the group is a nitrogen atom, the preferred embodiment of the group in formula (4) is the structure of formulas (32) to (39):

[0096]

[0097]

[0098] The symbols have the definitions given above.

[0099] Particularly preferred are the six-membered aromatic rings and heteroaromatic rings of formulas (15) to (19) described above. Very particularly preferred are the o-phenylene groups, i.e., the groups of formula (15) above. Preferably, all R are H.

[0100] Simultaneously, adjacent R substituents can also form a ring system together, enabling the formation of fused structures, including fused aryl and heteroaryl groups, such as naphthalene, quinoline, benzimidazole, carbazole, dibenzofuran, or dibenzothiophene. Such ring formation in the groups of formula (15) above is schematically shown below, which can produce groups of formulas (15a) to (15j), for example:

[0101]

[0102] The symbols have the definitions given above.

[0103] Generally, fused groups can be fused to any position in the unit of formula (5), as shown by the fused benzo groups in formulas (15a) to (15c). Groups fused to the units of formula (5) in formulas (15d) to (15j) can therefore also be fused to other positions in the unit of formula (5).

[0104] The groups in formula (3) can more preferably be represented by formulas (3a) to (3m), and the groups in formula (4) can more preferably be represented by formulas (4a) to (4m):

[0105]

[0106]

[0107]

[0108] The symbols therein have the definitions given above. Preferably, X 2 It is the same or different in each case, and it is CR.

[0109] In a preferred embodiment of the invention, the groups of formulas (3a) to (3m) are selected from the groups of formulas (6a') to (6m'), and the groups of formulas (4a) to (4m) are selected from the groups of formulas (10a') to (10m'):

[0110]

[0111]

[0112]

[0113] The symbols therein have the definitions given above. Preferably, X 2 In each case it is the same or different, and it is CR, especially CH.

[0114] A particularly preferred embodiment of the group in formula (3) is the group in formula (6a):

[0115]

[0116] The symbols have the definitions given above.

[0117] More preferably, the R groups in the above formulas are the same or different, and are H, D, or alkyl groups having one to four carbon atoms. Most preferably, R = H. Therefore, the structure of the following formula (6a”') is particularly preferred:

[0118]

[0119] The symbols have the definitions given above.

[0120] The following describes a bidentate subligand in M ​​that is connected to a bridging base of formula (3) or formula (4) or the preferred embodiment described above.

[0121] The three bidentate subligands can be the same or different, and are preferably monoanionic. When the bidentate subligands are the same, they preferably also have the same substitution. When all three bidentate subligands are the same, this produces a C3-symmetric iridium complex when the unit of formula (3) or (4) also has C3 symmetry, which is advantageous in terms of ligand synthesis. It is also advantageous to select three bidentate subligands differently or to select two identical subligands and a different third subligand to produce a C1-symmetric metal complex, because this allows for a greater possible variation of the ligands so that the desired properties of the complex, such as the HOMO and LUMO positions or the luminescence color, can be more easily changed. Furthermore, the solubility of the complex can thus be improved without having to attach long aliphatic or aromatic groups that impart solubility. In a preferred embodiment of the invention, three bidentate subligands are selected identically or two of the bidentate subligands are selected identically and the third bidentate subligand is different from the first two bidentate subligands.

[0122] In another preferred embodiment of the invention, the coordinating atoms of the bidentate subligands are the same or different in each case, and are selected from C, N, P, O, S and / or B, more preferably from C, N and / or O, and most preferably from C and / or N. The bidentate subligands preferably have 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. In this case, the coordinating atoms of each of the three subligands may be the same, or they may be different. Preferably, at least one of the bidentate subligands has one carbon atom and one nitrogen atom, or two carbon atoms as coordinating atoms, particularly one carbon atom and one nitrogen atom. More preferably, at least two of the bidentate subligands have one carbon atom and one nitrogen atom, or two carbon atoms as coordinating atoms, particularly one carbon atom and one nitrogen atom. Most preferably, all three bidentate subligands have one carbon atom and one nitrogen atom, or two carbon atoms as coordinating atoms, particularly one carbon atom and one nitrogen atom. Therefore, iridium complexes are particularly preferred, wherein all three bidentate subligands are ortho-metallized, i.e., forming a metal ring compound with iridium, wherein at least one iridium-carbon bond is present.

[0123] The metal ring compound formed by iridium and bidentate subligands is further preferred when it is a five-membered ring, particularly when the coordinating atoms are C and N, N and N, or N and O. Six-membered metal ring compounds are also preferred when the coordinating atom is O. This is illustrated schematically below:

[0124]

[0125] Where N is the coordinating nitrogen atom, C is the coordinating carbon atom, and O represents the coordinating oxygen atom, and the carbon atom shown is a bidentate ligand atom.

[0126] In a preferred embodiment of the invention, at least one of the bidentate subligands, more preferably at least two of the bidentate subligands, and most preferably all three bidentate subligands are the same or different in each case, and are selected from the structures of the following formulas (L-1), (L-2), and (L-3):

[0127]

[0128] The dashed bond represents the bond between the subligand and the bridging base of formula (3) or formula (4) or a preferred embodiment, and the other symbols used are as follows:

[0129] CyC is the same or different in each case, and is a substituted or unsubstituted aryl or heteroaryl group having 5 to 14 aromatic ring atoms, each of which is coordinated with a metal via a carbon atom and in each case is covalently bonded to CyD;

[0130] CyD is the same or different in each case, and is a substituted or unsubstituted heteroaryl group having 5 to 14 aromatic ring atoms and being coordinated with a metal via a nitrogen atom or via a carbene carbon atom and covalently bonded to CyC;

[0131] Furthermore, two or more of the optional substituents may together form a ring system; in addition, the optional groups are preferably selected from the aforementioned R groups.

[0132] Meanwhile, in the subligands of formulas (L-1) and (L-2), the CyD is preferably coordinated via an uncharged nitrogen atom or via a carbene carbon atom, particularly via an uncharged nitrogen atom. More preferably, in the ligand of formula (L-3), one of the two CyD groups is coordinated via an uncharged nitrogen atom, and the other of the two CyD groups is coordinated via an anionic nitrogen atom. Even more preferably, in the subligands of formulas (L-1) and (L-2), the CyC is coordinated via an anionic carbon atom.

[0133] When two or more of the substituents, particularly two or more R groups, form a ring system together, the ring system can be formed by substituents bonded to directly adjacent carbon atoms. Furthermore, it is also possible for the substituents on CyC and CyD in formulas (L-1) and (L-2), or the substituents on the two CyD groups in formula (L-3), to form a ring together. Therefore, the CyC group and the CyD group, or two CyD groups, can also form a single fused aryl or heteroaryl group as a bidentate ligand.

[0134] In a preferred embodiment of the invention, CyC is an aryl or heteroaryl group having 6 to 13 aromatic ring atoms, more preferably 6 to 10 aromatic ring atoms, and most preferably 6 aromatic ring atoms, particularly a phenyl group, which can be substituted by one or more R groups and covalently bonded to CyD via carbon atom coordination with a metal.

[0135] Preferred embodiments of the CyC group are structures of formulas (CyC-1) to (CyC-20):

[0136]

[0137] In each case, CyC binds to the position indicated by # in CyD and coordinates with the metal at the position indicated by *. R has the definition given above, and the other symbols used are as follows:

[0138] X is either the same or different in each case, and is CR or N, provided that there are no more than two symbols X in each ring that are N;

[0139] W is NR, O, or S;

[0140] The prerequisite is that when the bridging group of formula (3) or formula (4) or the preferred embodiment is bonded to CyC, a symbol X is C and the bridging group of formula (3) or formula (4) or the preferred embodiment is bonded to that carbon atom. Furthermore, the prerequisite is that when an Ar group is bonded to CyC, a symbol X is C and an Ar group is bonded to that carbon atom. When a CyC group is bonded to the bridging group of formula (3) or formula (4) or the preferred embodiment, the bond is preferably via the position marked with "o" in the formula described above, and therefore, the symbol X marked with "o" is preferably C in this case. The structure described above without any symbol X marked with "o" is preferably not directly bonded to the bridging group of formula (3) or formula (4) or the preferred embodiment, because such a bond with the bridging group is disadvantageous for steric reasons.

[0141] Preferably, no more than one symbol X in CyC is N, more preferably, all symbols X are CR, provided that when the bridging group of formula (3) or formula (4) or preferred embodiment is bonded to CyC, one symbol X is C and the bridging group of formula (3) or formula (4) or preferred embodiment is bonded to the carbon atom, and when the Ar group is bonded to CyC, one symbol X is C and the Ar group is bonded to the carbon atom.

[0142] Particularly preferred CyC groups are those of formulas (CyC-1a) to (CyC-20a):

[0143]

[0144]

[0145]

[0146] The symbols have the definitions given above, and when the bridging group of formula (3) or (4) or the preferred embodiment is bonded to CyC, an R group is absent and the bridging group of formula (3) or (4) or the preferred embodiment is bonded to the corresponding carbon atom, and furthermore, the prerequisite is that when the Ar group is bonded to CyC, an R group is absent and the Ar group is bonded to the corresponding carbon atom. When the CyC group is bonded to the bridging group of formula (3) or (4) or the preferred embodiment, the bond is preferably via the position marked with "o" in the formula described above, and therefore, the R group at that position is preferably absent in this case. The structure described above that does not contain any carbon atom marked with "o" is preferably not directly bonded to the bridging group of formula (3) or (4) or the preferred embodiment.

[0147] Among the (CyC-1) to (CyC-20) groups, preferred groups are (CyC-1), (CyC-3), (CyC-8), (CyC-10), (CyC-12), (CyC-13), and (CyC-16), with particularly preferred groups being (CyC-1a), (CyC-3a), (CyC-8a), (CyC-10a), (CyC-12a), (CyC-13a), and (CyC-16a).

[0148] In another preferred embodiment of the invention, CyD is a heteroaryl group having 5 to 13 aromatic ring atoms, more preferably 6 to 10 aromatic ring atoms, which is coordinated with a metal via an uncharged nitrogen atom or via a carbene carbon atom, and may be substituted by one or more R groups and covalently bonded to CyC.

[0149] Preferred embodiments of the CyD group are structures of formulas (CyD-1) to (CyD-14):

[0150]

[0151] In each case, the CyD group is bound to the CyC at the position indicated by # and coordinated with the metal at the position indicated by *, and X, W, and R have the definitions given above, provided that when the bridging group of formula (3) or (4) or the preferred embodiment is bonded to CyD, a symbol X is C and the bridging group of formula (3) or (4) or the preferred embodiment is bonded to the carbon atom, and further, provided that when the Ar group is bonded to CyD, a symbol X is C and the Ar group is bonded to the carbon atom. When the CyD group is bonded to the bridging group of formula (3) or (4) or the preferred embodiment, the bond is preferably via the position marked by “o” in the formula described above, and therefore, the symbol X marked by “o” is preferably C in this case. The structure described above without any symbol X marked with "o" is preferably not directly bonded to the bridging base of formula (3) or formula (4) or the preferred embodiment, because such bonding with the bridging base is disadvantageous for spatial reasons.

[0152] In this case, the (CyD-1) group to the (CyD-4) group, the (CyD-7) group to the (CyD-10) group, the (CyD-13) group and the (CyD-14) group are coordinated with the metal via an uncharged nitrogen atom, the (CyD-5) group and the (CyD-6) group are coordinated with the metal via a carbene carbon atom, and the (CyD-11) group and the (CyD-12) group are coordinated with the metal via an anionic nitrogen atom.

[0153] Preferably, no more than one symbol X in CyD is N; more preferably, all symbols X are CR, provided that when the bridging group of formula (3) or formula (4) or the preferred embodiment is bonded to CyD, one symbol X is C and the bridging group of formula (3) or formula (4) or the preferred embodiment is bonded to that carbon atom. Furthermore, when an Ar group is bonded to CyD, one symbol X is C and the Ar group is bonded to that carbon atom.

[0154] Particularly preferred CyD groups are those of formulas (CyD-1a) to (CyD-14b):

[0155]

[0156] The symbols used have the definitions given above, and when the bridging group of formula (3) or formula (4) or the preferred embodiment is bonded to CyD, an R group is absent and the bridging group of formula (3) or formula (4) or the preferred embodiment is bonded to the corresponding carbon atom, and furthermore, the prerequisite is that when the Ar group is bonded to CyD, an R group is absent and the Ar group is bonded to the corresponding carbon atom. When the CyD group is bonded to the bridging group of formula (3) or formula (4) or the preferred embodiment, the bond is preferably via the position marked with "o" in the formula described above, and therefore, the R group at that position is preferably absent in this case. The structure described above without any carbon atom marked with "o" is preferably not directly bonded to the bridging group of formula (3) or formula (4) or the preferred embodiment. Furthermore, when the Ar group is bonded to CyD, a position is not replaced by an R group and the Ar group is bonded to that carbon atom.

[0157] Among the (CyD-1) to (CyD-14) groups, the preferred groups are (CyD-1), (CyD-2), (CyD-3), (CyD-4), (CyD-5), and (CyD-6), especially (CyD-1), (CyD-2), and (CyD-3), and particularly (CyD-1a), (CyD-2a), (CyD-3a), (CyD-4a), (CyD-5a), and (CyD-6a), especially (CyD-1a), (CyD-2a), and (CyD-3a).

[0158] In a preferred embodiment of the invention, CyC is an aryl or heteroaryl group having 6 to 13 aromatic ring atoms, and CyD is a heteroaryl group having 5 to 13 aromatic ring atoms. More preferably, CyC is an aryl or heteroaryl group having 6 to 10 aromatic ring atoms, and CyD is a heteroaryl group having 5 to 10 aromatic ring atoms. Most preferably, CyC is an aryl or heteroaryl group having 6 aromatic ring atoms, particularly a phenyl group, and CyD is a heteroaryl group having 6 to 10 aromatic ring atoms. CyC and CyD may be substituted with one or more R groups.

[0159] The preferred (CyC-1) to (CyC-20) groups and (CyD-1) to (CyD-14) groups described above can be combined with each other in the subligands of formulas (L-1) and (L-2) as desired, provided that at least one of the CyC or CyD groups has a suitable linking site with the bridging group of formula (3) or formula (4) or the preferred embodiment, the suitable linking site being indicated by “o” in the formulas given above. It is particularly preferred when the CyC group and CyD group (i.e., groups of formulas (CyC-1a) to (CyC-20a) and groups of formulas (CyD1-a) to (CyD-14b)) designated as particularly preferred above are combined with each other, provided that at least one of the preferred CyC group or CyD group has a suitable linking site with the bridging group of formula (3) or formula (4) or the preferred embodiment, and the suitable linking site is indicated by "o" in the formula given above. Combinations where neither CyC nor CyD has such a suitable linking site for the bridging group of formula (3) or formula (4) or the preferred embodiment are therefore not preferred.

[0160] It is particularly preferred when one of the (CyC-1) group, (CyC-3) group, (CyC-8) group, (CyC-10) group, (CyC-12) group, (CyC-13) group, and (CyC-16) group, especially one of the (CyC-1a) group, (CyC-3a) group, (CyC-8a) group, (CyC-10a) group, (CyC-12a) group, (CyC-13a) group, and (CyC-16a) group is combined with one of the (CyD-1) group, (CyD-2) group, and (CyD-3) group, especially with one of the (CyD-1a) group, (CyD-2a) group, and (CyD-3a) group.

[0161] The preferred subligand (L-1) has the structures of formulas (L-1-1) and (L-1-2), and the preferred subligand (L-2) has the structures of formulas (L-2-1) to (L-2-3):

[0162]

[0163] The symbols used have the definitions given above, * indicates the coordination position with iridium and “o” indicates the bond position with the bridging group of formula (3) or formula (4) or preferred embodiment, provided that when the Ar group is bonded to the subligand, a symbol X is C and the Ar group is bonded to the carbon atom.

[0164] The particularly preferred subligand (L-1) has the structures of formulas (L-1-1a) and (L-1-2b), and the particularly preferred subligand (L-2) has the structures of formulas (L-2-1a) to (L-2-3a):

[0165]

[0166] The symbols used have the definitions given above, and “o” indicates the position of the bond with the bridging group of formula (3) or formula (4) or preferred embodiment, provided that when the Ar group is bonded to the subligand, an R group is not present and the Ar group is bonded to the carbon atom.

[0167] The preferred CyD groups in the subligands of formula (L-3) can also be combined with each other as desired. Preferably, uncharged CyD groups (i.e., (CyD-1) to (CyD-10) groups, (CyD-13) groups or (CyD-14) groups) are combined with anionic CyD groups (i.e., (CyD-11) groups or (CyD-12) groups), provided that at least one of the preferred CyD groups has a suitable linking site with the bridging group of formula (3) or formula (4) or the preferred embodiment. The suitable linking site is indicated by "o" in the formula given above.

[0168] When two R groups (in formulas (L-1 and (L-2), one of them is bonded to CyC and the other to CyD; or in formula (L-3), one of them is bonded to a CyD group and the other to another CyD group) form an aromatic ring system with each other, this can produce bridged subligands and, for example, subligands that collectively represent a single, larger heteroaryl group, such as benzo[h]quinoline, etc. The ring formation between the substituents on CyC and CyD in formulas (L-1) and (L-2) or between the substituents on the two CyD groups in formula (L-3) is preferably achieved via a group according to one of formulas (40) to (49):

[0169]

[0170] Where R 1 With the definitions given above, and the dashed bond indicating a bond with CyC or CyD. Meanwhile, asymmetric groups among those groups can be incorporated in each of two possible orientations; for example, in the group of formula (49), the oxygen atom can be bonded to the CyC group and the carbonyl group can be bonded to the CyD group, or the oxygen atom can be bonded to the CyD group and the carbonyl group can be bonded to the CyC group. Additionally, the Ar group can also be bonded to one of these groups.

[0171] Meanwhile, the group of formula (46) is preferred, especially when this causes ring formation to obtain a six-membered ring, which is shown below for example by formulas (L-22) and (L-23).

[0172] Preferred ligands produced via ring formation between two R groups in different rings are those of formulas (L-4) to (L-31) shown below:

[0173]

[0174]

[0175]

[0176] The symbols used have the definitions given above, and “o” indicates the position where the subligand is bonded to a group of formula (3) or formula (4) or preferred embodiment, provided that when the Ar group is bonded to the subligand, a symbol X is C and the Ar group is bonded to the carbon atom.

[0177] In a preferred embodiment of the subligands of formulas (L-4) to (L-31), one symbol X is N and the other symbols X are CR, or all symbols X are CR, provided that when the Ar group is bonded to the subligand, one symbol X is C and the Ar group is bonded to the carbon atom.

[0178] In another embodiment of the invention, it is preferred if, in groups (CyC-1) to (CyC-20) or (CyD-1) to (CyD-14) or in the subligands (L-1-1) to (L-2-3) and (L-4) to (L-31), one of atom X is N, and the R group bonded as a substituent adjacent to the nitrogen atom is not hydrogen or deuterium. This similarly applies to preferred structures (CyC-1a) to (CyC-20a) or (CyD-1a) to (CyD-14b), wherein the substituent bonded to the non-coordinated nitrogen atom is preferably an R group that is not hydrogen or deuterium. This substituent R is preferably selected from groups including: CF3, OCF3, OR 1 The R group comprises an alkyl group having 1 to 10 carbon atoms, particularly a branched or cyclic alkyl group having 3 to 10 carbon atoms, an aromatic ring system or a heteroaromatic ring system or an aralkyl group or a heteroaromatic group. These groups are spatially required. It is also preferred that the R group can form a ring with an adjacent R group.

[0179] Another suitable bidentate subligand is a subligand of formula (L-32) or formula (L-33):

[0180]

[0181] Where R has the definition given above, * indicates the position of coordination with the metal, "o" indicates the connection position of the subligand with the group of formula (3) or formula (4) or preferred embodiment, and other symbols used are as follows:

[0182] X is the same or different in each case, and is CR or N, provided that no more than one symbol X is N in each ring, and further provided that one symbol X is C and the group of formula (3) or formula (4) or preferred embodiment is bonded to the carbon atom, and further provided that when the Ar group is bonded to the subligand, one symbol X is C and the Ar group is bonded to the carbon atom.

[0183] When two R groups bonded to adjacent carbon atoms in the subligands (L-32) and (L-33) form an aromatic ring with each other, the ring together with the two adjacent carbon atoms preferably has the structure of formula (50):

[0184]

[0185] The dashed bond indicates the linkage of the group within the ligand, and Y is either the same or different in each case and is CR. 1 Or N, and preferably no more than one symbol Y is N. Additionally, the Ar group can also be bonded to this group.

[0186] In a preferred embodiment of the subligand (L-32) or (L-33), there is no more than one group of formula (50). The subligand is therefore preferably a subligand of formulas (L-34) to (L-39):

[0187]

[0188] Where X is the same or different in each case and is CR or N, but the R groups together do not form an aromatic ring system or a heteroaromatic ring system, and the other symbols have the definitions given above, provided that when the Ar group is bonded to the subligand, a symbol X is C and the Ar group is bonded to the carbon atom.

[0189] In a preferred embodiment of the invention, in the subligands of formulas (L-32) to (L-39), a total of 0, 1, or 2 of the symbols X and Y (if present) are N. More preferably, a total of 0 or 1 of the symbols X and Y (if present) are N.

[0190] In a preferred embodiment of the invention, the X group ortho-coordinated with the metal is CR. In this group, the R bonded ortho-coordinated with the metal is preferably selected from H, D, F, and methyl.

[0191] In another embodiment of the invention, it is preferred if one of atom X or atom Y (if present) is N, and the substituent bonded to the nitrogen atom is an R group that is not hydrogen or deuterium. The substituent R is preferably selected from the following groups: CF3, OCF3, OR. 1 The R group comprises an alkyl group having 1 to 10 carbon atoms, particularly a branched or cyclic alkyl group having 3 to 10 carbon atoms, an aromatic ring system or a heteroaromatic ring system or an aralkyl group or a heteroaromatic group. These groups are spatially required. It is also preferred that the R group can form a ring with an adjacent R group.

[0192] Other suitable bidentate subligands are structures of formulas (L-40) to (L-44), wherein preferably, no more than one of the three bidentate subligands is one of the structures:

[0193]

[0194] Subligands (L-40) to (L-42) are each coordinated to the metal via a clearly indicated nitrogen atom and a negatively charged oxygen atom, and subligands (L-43) and (L-44) are coordinated to the metal via two oxygen atoms. X has the definition given above, and “o” indicates the position of the subligand connected to a group of formula (3) or formula (4) or a preferred embodiment, provided that when the Ar group is bonded to the subligand, a symbol X is C and the Ar group is bonded to the carbon atom.

[0195] The preferred embodiments of X described above are also preferred for subligands of formulas (L-40) to (L-42). The preferred subligands of formulas (L-40) to (L-42) are therefore subligands of formulas (L-40a) to (L-42a):

[0196]

[0197] The symbols used have the definitions given above, and “o” indicates the position where the subligand is attached to a group of formula (3) or formula (4) or a preferred embodiment, provided that when the Ar group is bonded to the subligand, an R group is not present and the Ar group is bonded to the corresponding carbon atom.

[0198] More preferably, in these formulas, R is hydrogen, where “o” indicates the position where the subligand is attached to the group of formula (3) or formula (4) or the preferred embodiment, and therefore, the structure is the structure of formulas (L-40b) to (L-42b):

[0199]

[0200] The symbols used have the definitions given above.

[0201] In another preferred embodiment of the invention, the complex M is an iridium complex, wherein it may be coordinated with one iridium atom by three identical or different bidentate ligands. In this case, -[[[Ar] p -B] m -R B The group binds to one of these three bidentate ligands, or if more than one such group is present, then -[[[Ar]] p -B] m -R B The group also binds to two or three of the bidentate ligands.

[0202] The bidentate ligand is preferably selected from the structures of the following formulas (L-1') and (L-3'):

[0203]

[0204] The symbols have the definitions given above.

[0205] In this context, the same preferred embodiments described above for subligands (L-1), (L-2) and (L-3) apply to ligands of formula (L-1') and formula (L-3'), except that ligands of formula (L-1') and formula (L-3') are not bonded to the bridging group of formula (3) or formula (4).

[0206] In another preferred embodiment of the invention, M is an organometallic platinum complex. When M is an organometallic platinum complex having two bidentate ligands, these may be the same or different and are preferably selected from the ligands of formulas (L-1') and (L-3') described above, wherein the above-described preferred options also apply.

[0207] When M is an organometallic platinum complex with tetradentate ligands, this can be schematically represented by the following formula (Lig'):

[0208]

[0209] V' is preferably selected from CR2, NR, O, S, and BR, more preferably from CR2 and NR, wherein R has the definition given above, and L1 and L2 are the same or different in each case and are each a bidentate subligand, preferably a monoanion bidentate subligand. Since the ligand has two bidentate subligands, the overall result is a tetradentate ligand, i.e., a ligand that coordinates or binds to platinum via four coordination sites. In this case, L1 and L2 are preferably those structures specified above by formulas (L-1), (L-2), and (L-3) or preferred structures.

[0210] The platinum complex M formed with the ligand of this formula (Lig') can therefore be schematically represented by the following formula:

[0211]

[0212] The symbols used have the definitions given above.

[0213] Preferred substituents that can be present on the aforementioned subligands and ligands, and also on the divalent aromatic or heteroaromatic substituents in the structure of formula (5), are described below.

[0214] In a preferred embodiment of the invention, the metal complex of the invention contains two R substituents that are bonded to adjacent carbon atoms and together form an aliphatic ring according to one of the formulas described below. In this case, the two R substituents forming the aliphatic ring may be present on the bridging group of formula (3) or formula (4) or the preferred embodiment and / or on one or more of the bidentate subligands. The aliphatic ring formed by the two R substituents forming a ring together is preferably described by one of the following formulas (51) to (57):

[0215]

[0216] Where R 1 and R 2 As defined above, a dashed bond represents the connection of two carbon atoms in a ligand, and furthermore:

[0217] Z 1 Z 3 It is the same or different in each case, and is C(R) 3 )2, O, S, NR 3 Or C (=O);

[0218] Z 2 It is C(R) 1 )2, O, S, NR 3 Or C (=O);

[0219] G is an alkylene group, which has one, two, or three carbon atoms and can be divided by one or more R atoms. 2 Group substitution; -CR 2 =CR 2 -; or ortho-bonded arylene or heteroarylene, having 5 to 14 aromatic ring atoms and capable of being bonded by one or more R 2 Group substitution;

[0220] R 3 In each case, it may be the same or different, and is H, F, a straight-chain alkyl or alkoxy group having 1 to 10 carbon atoms, or a branched or cyclic alkyl or alkoxy group having 3 to 10 carbon atoms, wherein the alkyl or alkoxy group in each case may be one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by R 2 C = CR 2 C≡C, Si(R) 2 2. C=O, NR 2 O, S or CONR 2 Replacement, or an aromatic ring system or heteroaromatic ring system having 5 to 24 aromatic ring atoms and in each case can be replaced by one or more R 2 Group substitution, or aryloxy or heteroaryloxy groups having 5 to 24 aromatic ring atoms and being capable of being substituted by one or more R groups. 2 Group substitution; simultaneously, two R atoms bonded to the same carbon atom 3 Groups can combine to form aliphatic or aromatic ring systems and thus spirocyclic systems; furthermore, R 3 With adjacent R or R 1 Groups can form aliphatic ring systems;

[0221] The prerequisite is that no two heteroatoms in these groups are directly bonded to each other, and no two C=O groups are directly bonded to each other.

[0222] In a preferred embodiment of the present invention, R 3 Not H.

[0223] In the structures of formulas (51) to (57) described above, and in other embodiments of these structures designated as preferred, the double bond is depicted formally between two carbon atoms. This is a simplification of the chemical structure when these two carbon atoms are incorporated into an aromatic or heteroaromatic system, and thus the bond between these two carbon atoms is formally between the bonding level of a single bond and that of a double bond. The depiction of the formal double bond should therefore not be interpreted as limiting the structure; rather, it will be apparent to those skilled in the art that this is an aromatic bond.

[0224] When adjacent groups in the structure of the present invention form an aliphatic ring system, it is preferred that the latter does not contain any acidic benzylic protons. A benzylic proton is understood to mean a proton bonded directly to a carbon atom bonded to a ligand. This can be achieved because the carbon atom in the aliphatic ring system directly bonded to the aryl or heteroaryl group is fully substituted and contains no bonded hydrogen atoms. Therefore, the absence of acidic benzylic protons in formulas (50) to (52) is due to Z 1 and Z 3 In them, C(R) 3 )2 is defined such that R 3 This is not achieved by hydrogen. It can also be achieved because the carbon atom in the aliphatic ring system directly bonded to the aryl or heteroaryl group is a bridgehead in a bicyclic or polycyclic structure. The proton bonded to the bridgehead carbon atom has significantly lower acidity than the benzylic protons not bonded to carbon atoms within the bicyclic or polycyclic structure due to the spatial structure of the bicyclic or polycyclic structure, and is considered a non-acidic proton in the context of this invention. Therefore, the absence of acidic benzylic protons in formulas (53) to (57) is due to the bicyclic structure, and thus, R 1 When it is H, the corresponding anion of the bicyclic structure is not mediatically stabilized and has a much lower acidity than the benzylic proton. Even when R in equations (53) to (57) 1 When it is H, it is therefore a non-acid proton in the context of this application.

[0225] In a preferred embodiment of the structure of equations (51) to (57), Z 1 Group, Z 2 Groups and Z 3 No more than one of the groups is a heteroatom, especially O or NR. 3 And the other groups are C(R) 3 )2 or C(R 1 )2, or Z 1 and Z 3 In each case it is the same or different and is O or NR 3 And Z 2 It is C(R) 1 )2. In a particularly preferred embodiment of the present invention, Z 1 and Z 3 It is the same or different in each case and is C(R) 3 )2, and Z 2 It is C(R) 1 )2 and more preferably C(R) 3 )2 or CH 2 .

[0226] Preferred embodiments of formula (51) are therefore the structures of formulas (51-A), (51-B), (51-C), and (51-D), and a particularly preferred embodiment of formula (51-A) is the structure of formulas (51-E) and (51-F):

[0227]

[0228] Where R 1 and R 3 It has the definition given above, and Z 1 Z 2 and Z 3 In each case it is the same or different and is O or NR 3 .

[0229] The preferred embodiment of formula (52) is the structure of formulas (52-A) to (52-F):

[0230]

[0231] Where R 1 and R 3 It has the definition given above, and Z 1 Z 2 and Z 3 In each case it is the same or different and is O or NR 3 .

[0232] The preferred embodiment of formula (53) is the structure of formulas (53-A) to (53-E) below:

[0233]

[0234] Where R 1 and R 3 It has the definition given above, and Z 1 Z 2 and Z 3 In each case it is the same or different and is O or NR 3 .

[0235] In a preferred embodiment of the structure of equation (54), R is bonded to the bridge abutment. 1 The functional group is H, D, F, or CH3. More preferably, Z... 2 It is C(R) 1 )2 or O, and more preferably C(R) 3 2. Preferred embodiments of formula (54) are therefore the structures of formulas (54-A) and (54-B), and a particularly preferred embodiment of formula (54-A) is the structure of formula (54-C):

[0236]

[0237] The symbols used have the definitions given above.

[0238] In a preferred embodiment of the structures of equations (55), (56), and (57), the R bonded to the bridge abutment 1 The functional group is H, D, F, or CH3. More preferably, Z2 is C(R) 1 2. Preferred embodiments of equations (55), (56), and (57) are therefore the structures of equations (55-A), (56-A), and (57-A):

[0239]

[0240] The symbols used have the definitions given above.

[0241] Preferably, the G group in formulas (54), (54-A), (54-B), (54-C), (55), (55-A), (56), (56-A), (57), and (57-A) is a 1,2-ethylidene group, which can be mediated by one or more R groups. 2 Group substitution, wherein R 2 Preferably, they are the same or different in each case, and are H or an alkyl group having 1 to 4 carbon atoms, or an o-arylene group having 6 to 10 carbon atoms and can be substituted by one or more R groups. 2 The group is substituted, but preferably unsubstituted, and in particular, it can be substituted by one or more R2 groups, but preferably unsubstituted o-phenylene groups.

[0242] In another preferred embodiment of the invention, in the groups of formulas (51) to (57) and in the preferred embodiment R 3 In each case, it may be the same or different, and is F, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein one or more non-adjacent CH2 groups may be R in each case. 2 C = CR 2 The substitution can be made by replacing one or more hydrogen atoms with D or F, or by an aromatic ring system or a heteroaromatic ring system having 5 to 14 aromatic ring atoms and in each case being substituted by one or more R2 groups; simultaneously, two R3 groups bonded to the same carbon atom can together form an aliphatic ring system or an aromatic ring system and thus form a spirocyclic system; furthermore, R3 can be substituted with adjacent R or R 1The groups form aliphatic ring systems.

[0243] In a particularly preferred embodiment of the invention, in the groups of formulas (51) to (57) and in the preferred embodiment, R 3 In each case, it may be the same or different, and is F, a straight-chain alkyl group having 1 to 3 carbon atoms, particularly methyl, or an aromatic ring system or heteroaromatic ring system having 5 to 12 aromatic ring atoms and in each case may be one or more R 2 The group is substituted, but preferably unsubstituted; at the same time, two R groups bonded to the same carbon atom... 3 Groups can combine to form aliphatic or aromatic ring systems and thus spirocyclic systems; furthermore, R 3 It can be with adjacent R or R 1 The groups form aliphatic ring systems.

[0244] Examples of particularly suitable groups of formula (51) are those described below:

[0245]

[0246]

[0247] Examples of particularly suitable groups of formula (52) are those described below:

[0248] Examples of particularly suitable groups of formulas (53), (56) and (57) are the groups described below:

[0249]

[0250] Examples of particularly suitable groups of formula (54) are those described below:

[0251]

[0252] Examples of particularly suitable groups of formula (55) are those described below:

[0253]

[0254] When the R group is bonded to a bidentate subligand or ligand, or to a divalent aromatic or heteroaromatic group of formula (5) in formula (3) or (4) or preferred embodiments, these R groups are the same or different in each case and are preferably 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 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl or alkenyl group in each case may be one or more R 1 Group substitution, or an aromatic ring system or heteroaromatic ring system having 5 to 30 aromatic ring atoms and in each case being substituted with one or more R groups. 1 Group substitution; simultaneously, two adjacent R groups together or R together with R 1 Together, they can form monocyclic or polycyclic aliphatic or aromatic ring systems. More preferably, these R groups are the same or different in each case and are selected from H, D, F, N (R 1 2, a straight-chain alkyl group having 1 to 6 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein one or more hydrogen atoms may be replaced by D or F, or an aromatic ring system or a heteroaromatic ring system having 5 to 24, preferably 6 to 24, more preferably 6 to 13 aromatic ring atoms, and in each case may be replaced by one or more R 1 Group substitution; simultaneously, two adjacent R groups together or R together with R 1 Together, they can form monocyclic or polycyclic aliphatic or aromatic ring systems.

[0255] Preferred R bonded to R 1 The functional groups are either the same or different in each case, and are H, D, F, N(R) 2 )2, CN, a straight-chain alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl group in each case may be one or more R 2 Group substitution, or an aromatic ring system or heteroaromatic ring system having 5 to 24 aromatic ring atoms and in each case being substituted by one or more R groups. 2 Group substitution; simultaneously, two or more adjacent R groups... 1 The groups can together form monocyclic or polycyclic aliphatic ring systems. A particularly preferred R is the one bonded to R. 1 The groups are the same or different in each case, and are H, F, CN, straight-chain alkyl groups having 1 to 5 carbon atoms or branched or cyclic alkyl groups having 3 to 5 carbon atoms, each of which can be substituted by one or more R groups. 2 Group substitution, or an aromatic ring system or heteroaromatic ring system having 5 to 13, preferably 6 to 13, aromatic ring atoms, and in each case can be replaced by one or more R groups.2 Group substitution; simultaneously, two or more adjacent R groups... 1 Groups can come together to form monocyclic or polycyclic aliphatic ring systems.

[0256] Preferred R 2 The functional group is the same or different in each case and is H, F, or an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms; at the same time, two or more R 2 Substituents can also form monocyclic or polycyclic aliphatic ring systems together.

[0257] The following describes the invention - [[Ar]] p -B-[Ar] q ] m -R B In a preferred embodiment of the substituent, when q = 0, it is the substituent -[[Ar] p -B] m -R B .

[0258] As mentioned above, Ar is a linearly bonded arylene or heteroaryl group having 6 to 30 aromatic ring atoms and can be substituted by one or more R groups.

[0259] In the context of this invention, linearly bonded arylene or heteroarylene is understood to mean para-bonded six-membered arylene or heteroarylene. The same applies when another group is fused with this group, such as in, for example, 1,4-bonded naphthalene. The same also applies when the Ar group formally contains multiple six-membered arylene or heteroarylene, such as in, for example, 2,7-bonded fluorene, correspondingly bonded indo[a]fluorene, or 2,7-bonded carbazole.

[0260] In a preferred embodiment of the invention, Ar may be the same or different in each case, and is selected from groups of formulas (Ar-1) to (Ar-10):

[0261]

[0262] The dashed lines indicate the connection of the groups, and the symbols used have the definitions given above. Preferably, no more than two symbols X are N for each Ar group; more preferably, no more than one symbol X is N for each Ar group, and the other symbols X are CR. Most preferably, all symbols X are CR, and therefore, the Ar groups are more preferably selected from formulas (Ar-1a) to (Ar-10a):

[0263]

[0264] The symbols used have the definitions given above.

[0265] As described above, the B group is a bicyclic or oligocyclic group of formula (2). In a preferred embodiment of the invention, Y 1 Y 2 and Y 3 In each case, they may be the same or different, preferably the same, and are CR2, CR2-CR2, CR2-CR2-CR2, CR2-CR2-CR2-CR2 or ortho-bonded phenylene groups, said phenylene group may be substituted by one or more R groups; Y 1 Group, Y 2 Groups and / or Y 3 The groups here can be linked to each other by single bonds or via R groups to form oligocyclic groups.

[0266] More preferably, Y 1 Group, Y 2 Group and Y 3 The groups are the same and are CH2, CH2-CH2, CH2-CH2-CH2, CH2-CH2-CH2-CH2 or unsubstituted o-phenylene groups.

[0267] Suitable and particularly preferred examples of groups of formula (2) are the structures (B-1) to (B-6) described below:

[0268]

[0269] The dashed bond in each case represents the connection of the group.

[0270] In a preferred embodiment of the invention, the substituent R B Selected from H, M, straight-chain alkyl groups having 1 to 10 carbon atoms or branched or cyclic alkyl groups having 3 to 10 carbon atoms, wherein the alkyl group in each case can be generated by one or more R 1 The group is substituted, but preferably unsubstituted, or an aromatic ring system or heteroaromatic ring system having 6 to 24 aromatic ring atoms and in each case can be substituted by one or more R groups. 1 Group substitution. More preferably, the substituent R B Selected from M, a straight-chain alkyl group having 1 to 6 carbon atoms or a branched or cyclic alkyl group having 3 to 6 carbon atoms, or an aromatic ring system having 6 to 12 aromatic ring atoms and capable of being converted by one or more R 1 The group is substituted, but preferably unsubstituted. When R BWhen it is M, the same preferred embodiments described above for another M group in the compounds of the present invention are applicable.

[0271] The compounds of this invention are chiral. Depending on the exact structure of the complex and ligands, the formation of diastereomers and pairs of enantiomers is feasible. The complexes of this invention comprise mixtures of different diastereomers or corresponding racemates and single, isolated diastereomers or enantiomers.

[0272] If mononuclear complex synthesis units are used to form the polynuclear complexes of the present invention, these are typically used in racemic forms of the Δ and Λ isomers. This produces diastereomeric mixtures of the polynuclear compounds of the present invention, such as the Δ,Δ / Λ,Λ and (meta-)Δ,Λ forms of dinuclear compounds. Unless otherwise stated, these are further converted or used as diastereomeric mixtures. Furthermore, these can be separated by chromatography or by fractional crystallization.

[0273] If the enantiomers of the mononuclear complex synthesis unit are used to form the polynuclear complexes of the present invention, then, for example, the dinuclear complexes in the form of Δ,Δ, Λ,Λ, or (meta-)Δ,Λ can be selectively prepared. This also applies to the trinuclear complexes and more advanced polynuclear complexes of the present invention.

[0274] The Δ or Λ isomer of the mononuclear complex synthesis unit required for this purpose can be obtained as follows. If C3 or C... 3v Symmetrical ligands typically yield racemic mixtures of C3 symmetric complexes, i.e., racemic mixtures of the Δ and Λ enantiomers. These can be separated by standard methods (chromatography on chiral materials / columns or optical resolution by crystallization). An example of a C3 symmetric ligand with three phenylpyridine subligands is shown in the scheme below, and similarly applies to all other C3 or C4 symmetric complexes. 3v Symmetrical ligands.

[0275]

[0276] Optical separation of diastereomeric salt pairs via stepwise crystallization can be achieved by conventional methods. One alternative for this purpose is to oxidize the uncharged Ir(III) complex (e.g., using peroxides or H₂O₂ or by electrochemical means), add an enantiomeric pure monoanionic base (chiral base) salt to the resulting cationic Ir(IV) complex, separate the resulting diastereomeric salts by stepwise crystallization, and then reduce them with a reducing agent (e.g., zinc, hydrazine hydrate, ascorbic acid, etc.) to obtain the enantiomeric pure uncharged complex, as illustrated schematically below:

[0277]

[0278] Furthermore, it is feasible to synthesize enantiomers in pure or enriched form by complexation in a chiral medium (e.g., R-1,1-binaphthol or S-1,1-binaphthol).

[0279] In C s A similar method can be used for complexes of symmetrical ligands.

[0280] If a C1 symmetrical ligand is used in the complexation, then what is usually obtained is a diastereomeric mixture of the complex, which can be separated by standard methods (chromatography, crystallization).

[0281] Enantiomerically pure C3 symmetrical complexes can also be synthesized selectively, as shown in the following scheme. For this purpose, enantiomerically pure C3 symmetrical ligands are prepared and complexed, the resulting diastereomeric mixture is isolated, and then the chiral groups are removed.

[0282]

[0283] Finally, the Δ or Λ isomer of the mononuclear complex synthesis unit obtained therefrom can be functionalized, for example, by halogenation or boronization, and then linked by a coupling reaction, such as Suzuki coupling, to obtain the polynuclear complex of the present invention.

[0284] The preferred embodiments described above can be combined with each other as desired. In a particularly preferred embodiment of the invention, all the preferred embodiments described above are applicable simultaneously.

[0285] The complexes of this invention can be prepared via two routes. First, ligands containing bicyclic or polycyclic unit B (2-dentate, 4-dentate, 6-dentate, 8-dentate, 10-dentate, or 12-dentate) can be prepared and then coordinated with one or more metals or one or more metal fragments. Generally, for this purpose, an iridium or platinum salt is reacted with the corresponding free ligand.

[0286] Therefore, the present invention also provides a method for preparing the iridium complex of the present invention, the method being carried out by reacting the corresponding 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).

[0287]

[0288] Wherein R has the definition given above, Hal = F, Cl, Br or I, and the iridium reactant may also be in the form of the corresponding hydrate. R is preferably an alkyl group having 1 to 4 carbon atoms.

[0289] Iridium compounds with alkoxide and / or halide and / or hydroxyl and diketide groups can also be used. These compounds can also be charged. Relevant iridium compounds particularly suitable as reactants are disclosed in WO 2004 / 085449. Particularly suitable are [IrCl2(acac)2]-, such as Na[IrCl2(acac)2]; metal complexes having acetylacetonate derivatives as ligands, such as Ir(acac)3 or tris(2,2,6,6-tetramethylheptane-3,5-diketone)iridium, and IrCl3·xH2O, where x is typically a number from 2 to 4.

[0290] The synthesis of the complex is preferably carried out as described in WO 2002 / 060910 and WO 2004 / 085449. In this case, the synthesis can also be activated, for example, by thermal or photochemical means and / or by microwave radiation. Furthermore, the synthesis can also be carried out in an autoclave at elevated pressure and / or elevated temperature.

[0291] The reaction can be carried out without adding solvents or melt additives to the melt of the corresponding ligand to be metallized at the ortho position. Optionally, solvents or melt additives may be added. Suitable solvents are protic or aprotic solvents, such as aliphatic and / or aromatic alcohols (methanol, ethanol, isopropanol, tert-butanol, etc.), oligohydric and polyhydric alcohols (ethylene glycol, 1,2-propanediol, glycerol, etc.), alcohol ethers (ethoxyethanol, diethylene glycol, triethylene glycol, polyethylene glycol, etc.), ethers (diethylene glycol dimethyl ether and triethylene glycol dimethyl ether, diphenyl ether, etc.), aromatic hydrocarbons, heteroaromatic hydrocarbons and / or aliphatic hydrocarbons (toluene, xylene, mesitylene, chlorobenzene, pyridine, dimethylpyridine, quinoline, isoquinoline, tridecane, hexadecane, etc.), amides (DMF, DMAC, etc.), lactams (NMP), sulfoxides (DMSO), or sulfones (dimethyl sulfone, sulfolane, etc.). Suitable melt additives are compounds that are solid at room temperature but melt and dissolve the reactants when the reaction mixture is heated to form a homogeneous melt. Particularly suitable are biphenyl, m-terphenyl, triphenyl, R-binaphthol or S-binaphthol or their corresponding racemic mixtures, 1,2-diphenoxybenzene, 1,3-diphenoxybenzene or 1,4-diphenoxybenzene, triphenylphosphine oxide, 18-crown-6, phenol, 1-naphthol, hydroquinone, etc. Hydroquinone is particularly preferred here.

[0292] Alternatively, one or more metal complexes functionalized with halogen, boric acid, or borate groups may be used with one or more appropriately functionalized [Ar] compounds. p -B]-R B The unit or a mixture thereof with functionalized Ar and B units is reacted in a coupling reaction (preferably Suzuki coupling) to obtain the compounds of the present invention. Further details in this regard can be inferred from the examples.

[0293] These methods can be used to further purify, if necessary, by recrystallization or sublimation, to obtain high purity of the compound of formula (1) of the present invention, preferably greater than 99% (determined by means of 1H NMR and / or HPLC).

[0294] The metal complexes of the present invention can also be made soluble by suitable substitutions, for example by relatively long alkyl groups (about 4 to 20 carbon atoms), particularly branched alkyl groups, or optionally substituted aryl groups, such as xylyl, mesitylene, or branched terphenyl or tetraphenyl. Another particular method that results in a significant increase in the solubility of the metal complexes is the use of fused aliphatic groups, such as those shown, for example, by formulas (51) to (57) disclosed above. These compounds are then soluble in a sufficient concentration at room temperature in standard organic solvents, such as toluene or xylene, to enable the complexes to be processed from solution. These soluble compounds are particularly suitable for processing from solution, for example by printing methods.

[0295] The compounds of the present invention can also be mixed with or covalently incorporated into polymers. This is particularly feasible in the case of compounds substituted with reactive leaving groups, such as bromine, iodine, chlorine, boric acid or borate esters, or with reactive polymerizable groups, such as olefins or oxetanes. These can be used as monomers for generating the corresponding oligomers, polymers or dendritic macromolecules. Oligopolymerization or polymerization is preferably achieved via halogen functional groups or boric acid functional groups or via polymerizable groups. In a preferred embodiment of the invention, the compounds of the present invention are used as end groups when they are used in oligomers, dendritic macromolecules or polymers.

[0296] The present invention therefore also provides oligomers, polymers, or dendritic macromolecules containing one or more of the compounds detailed above, wherein one or more of the compounds of the present invention are bonded to the polymer, oligomer, or dendritic macromolecule. The linkage of the compounds according to the invention thus forms a side chain of the oligomer or polymer, or is attached to the main chain, or constitutes an end group. The polymer, oligomer, or dendritic macromolecule may be conjugated, partially conjugated, or non-conjugated. The oligomer or polymer may be linear, branched, or dendritic. The repeating units of the compounds of the present invention in the oligomer, dendritic macromolecule, and polymer have the same preferred embodiments as described above.

[0297] To process the metal complexes of the present invention from the liquid phase, such as by spin coating or printing, formulations of the metal complexes of the present invention are required. These formulations can be, for example, solutions, dispersions, or emulsions. For this purpose, it is preferable to use a mixture of two or more solvents. Suitable and preferred solvents include, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, naphthol, veratrine, THF, methyl-THF, THP, chlorobenzene, dichlorobenzene, etc. Alkane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fenazine, 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, isopropylbenzene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, indene, NMP, p-isopropyltoluene, phenethyl ether 1,4-Diisopropylbenzene, diphenyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, 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.

[0298] The present invention also provides a formulation comprising at least one compound of the present invention and at least one additional compound. The additional compound may be, for example, a solvent, particularly one of the solvents described above or a mixture of these solvents. The additional compound may optionally be another organic or inorganic compound, which is also used in electronic devices, such as matrix materials. The additional compound may also be polymerized.

[0299] The metal complexes of the present invention described above, or the preferred embodiments detailed above, can be used as active components or oxygen sensitizers in electronic devices or photocatalysis. The present invention therefore also provides uses of the compounds of the present invention in electronic devices or as oxygen sensitizers or in photocatalysis. The present invention further provides an electronic device comprising at least one compound of the present invention.

[0300] Electronic devices are understood to mean any device comprising an anode, a cathode, and at least one layer containing at least one organic compound or organometallic compound. The electronic devices of the present invention therefore comprise an anode, a cathode, and at least one layer containing at least one metal complex of the present invention. Preferred electronic devices are selected from organic electroluminescent devices (OLEDs, PLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs) (the latter being understood to mean purely organic solar cells and dye-sensitized solar cells), organic optical detectors, organic photosensors, organic field quenching devices (O-FQDs), light-emitting electrochemical cells (LECs), oxygen sensors, and organic laser diodes (O-lasers), said devices containing at least one metal complex of the present invention in at least one layer. Organic electroluminescent devices are particularly preferred. The active component is generally an organic or inorganic material introduced between the anode and cathode, such as a charge-injecting material, a charge-transporting material, or a charge-blocking material, but particularly a luminescent material and a matrix material. The compounds of the present invention exhibit particularly good properties as luminescent materials in organic electroluminescent devices. A preferred embodiment of the present invention is therefore an organic electroluminescent device. Furthermore, the compounds of the present invention can be used to generate singlet oxygen or in photocatalysis. Particularly when the metal is ruthenium, it is preferred for use in dye-sensitized solar cells (“…”). Photosensitizer in batteries.

[0301] Organic electroluminescent devices include a cathode, an anode, and at least one light-emitting layer. In addition to these layers, it may also include other 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. It is also feasible that one or more hole transport layers are p-type doped, for example using metal oxides such as MoO3 or WO3 or using (per)fluorinated electron-deficient aromatic systems for p-type doping, and / or one or more electron transport layers are n-type doped. Intermediate layers can also be introduced between the two light-emitting layers, these intermediate layers having, for example, exciton blocking functions and / or controlling the charge balance in the electroluminescent device. However, it should be noted that not every one of these layers needs to be present.

[0302] In this context, the organic light-emitting device (OLED) may contain one emitting layer, or it may contain multiple emitting layers. If multiple emitting layers are present, these preferably have a total of multiple emission peaks between 380 nm and 750 nm, so that the overall result is white emission; in other words, multiple luminescent compounds that can fluoresce or phosphore are used in the emitting layers. Particularly preferred are three-layer systems in which the three layers exhibit blue, green, and orange or red emission (see, for example, WO 2005 / 011013 for basic construction), or systems with more than three emitting layers. The system may also be a hybrid system in which one or more layers fluoresce and one or more other layers phosphoresce. Tandem OLEDs are also particularly suitable for white-emitting OLEDs. White-emitting organic light-emitting devices can be used in lighting applications or in conjunction with color filters for full-color displays.

[0303] In a preferred embodiment of the present invention, the organic electroluminescent device comprises the metal complex of the present invention as a luminescent compound in one or more luminescent layers.

[0304] When the metal complex of the present invention is used as a luminescent compound in a luminescent layer, it is preferably used in combination with one or more matrix materials. Based on the overall mixture of the luminescent material and the matrix material, the mixture of the metal complex and the matrix material of the present invention contains 0.1% to 99% by weight, preferably 1% to 90% by weight, more preferably 3% to 40% by weight, and particularly 5% to 25% by weight of the metal complex of the present invention. Accordingly, based on the overall mixture of the luminescent material and the matrix material, the mixture contains 99.9% to 1% by weight, preferably 99% to 10% by weight, more preferably 97% to 60% by weight, and particularly 95% to 75% by weight of the matrix material.

[0305] The matrix material used can generally be any material known to be suitable for this purpose according to existing technology. Preferably, the triplet energy level of the matrix material is higher than that of the luminescent material.

[0306] Suitable matrix materials for the compounds used in this invention are ketones, phosphine oxides, sulfoxides, and sulfones, for example according to WO2004 / 013080, WO 2004 / 093207, WO 2006 / 005627, or WO 2010 / 006680; triarylamines, carbazole derivatives, such as CBP (N,N-biscarbazole biphenyl), m-CBP, or carbazole derivatives disclosed in WO 2005 / 039246, US2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851, or US 2009 / 0134784; indolecarbazole derivatives, for example according to WO 2007 / 063754 or WO 2008 / 056746; Indobenzocarbazole derivatives, for example according to WO2010 / 136109 or WO 2011 / 000455; Azacarbazole, for example according to EP 1617710, EP 1617711, EP1731584, JP 2005 / 347160; Bipolar matrix materials, for example according to WO 2007 / 137725; Silanes, for example according to WO2005 / 111172; Azaborane or borate esters, for example according to WO 2006 / 117052; Diazasilane derivatives, for example according to WO 2010 / 054729; Diazaphosphonane derivatives, for example according to WO 2010 / 054730; Triazine derivatives, for example according to WO 2010 / 015306, WO 2007 / 063754 or WO 2008 / 056746; zinc complexes, for example according to EP 652273 or WO 2009 / 062578; dibenzofuran derivatives, for example according to WO 2009 / 148015 or WO 2015 / 169412; or bridged carbazole derivatives, for example according to US 2009 / 0136779, WO 2010 / 050778, WO 2011 / 042107 or WO 2011 / 088877.

[0307] It is also preferable to use a variety of different matrix materials as a mixture, particularly at least one electron-conducting matrix material and at least one hole-conducting matrix material. Preferred combinations include, for example, using aromatic ketones, triazine derivatives, or phosphine oxide derivatives with triarylamine derivatives or carbazole derivatives as the mixed matrix of the metal complex of the present invention. It is also preferable to use a mixture of charge-transporting matrix materials and electroinert matrix materials, wherein the electroinert matrix materials are not significantly involved in (if any) charge transport, as described, for example, in WO 2010 / 108579. It is also preferable to use two electron-transporting matrix materials, such as triazine derivatives and lactam derivatives, as described, for example, in WO 2014 / 094964.

[0308] Another preferred method is to use a mixture of two or more triplet emitters and a matrix. In this case, the triplet emitter with a shorter wavelength emission spectrum is used as a co-matrix for the triplet emitter with a longer wavelength emission spectrum. For example, the metal complex of the present invention can be used as a co-matrix for a longer wavelength emitting triplet emitter, such as a green or red emitting triplet emitter. In this case, it is also preferred when both the shorter and longer wavelength emitting metal complexes are compounds of the present invention.

[0309] The metal complexes of the present invention can also be used for other functions in electronic devices, such as as hole transport materials in hole injection or transport layers, as charge generation materials, as electron blocking materials, as hole blocking materials, or as electron transport materials, for example, in electron transport layers. The metal complexes of the present invention can also be used as matrix materials for other phosphorescent metal complexes in light-emitting layers.

[0310] Preferred cathodes are metals, metal alloys, or multilayer structures composed of multiple metals with low work function, such as alkaline earth metals, alkali metals, main group metals, or lanthanides (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable are alloys composed of alkali metals or alkaline earth metals and silver, such as alloys composed of magnesium and silver. In the case of multilayer structures, in addition to the metals mentioned, other metals with relatively high work function, such as Ag, can be used. In this case, combinations of metals such as Mg / Ag, Ca / Ag, or Ba / Ag are generally used. It is also preferable to introduce a thin interlayer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. Examples of useful materials for this purpose are alkali metal fluorides or alkaline earth metal fluorides, and their corresponding oxides or carbonates (e.g., LiF, Li₂O, BaF₂, MgO, NaF, CsF, Cs₂CO₃, etc.). Organoalkali metal complexes, such as Liq (lithium hydroxyquinoline), are also useful for this purpose. The thickness of this layer is preferably 0.5 nm to 5 nm.

[0311] The preferred anode is a material with a high work function. Preferably, the anode has a work function greater than 4.5 eV relative to vacuum. Firstly, metals with high redox potentials are suitable for this purpose, such as Ag, Pt, or Au. Secondly, metal / metal oxide electrodes (e.g., Al / Ni / NiOx, Al / PtOx) are also preferred. For some applications, at least one of the electrodes must be transparent or partially transparent to allow irradiation of organic materials (O-SC) or light emission (OLED / PLED, O-laser). The preferred anode material here is a conductive mixed metal oxide. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Also preferred are conductive doped organic materials, especially conductive doped polymers, such as PEDOT, PANI, or derivatives of these polymers. This is further preferred when a p-type doped hole transport material is applied to the anode as a hole injection layer; in this case, suitable p-type dopants are metal oxides, such as MoO3 or WO3, or (per)fluorinated electron-deficient aromatic systems. Other suitable p-type dopants are HAT-CN (hexacyanohexaazabenzophenanthrene) or NPD9 from Novaled. This layer simplifies hole injection into materials with low HOMO, i.e., large HOMO in size.

[0312] In the other layers, any material used in the layers according to the prior art can generally be used, and those skilled in the art can combine any of these materials with the materials of the present invention in electronic devices without inventive effort.

[0313] The devices are structured accordingly (depending on the application), connected in contact, and ultimately hermetically sealed because the lifespan of these devices is severely shortened in the presence of water and / or air.

[0314] Another preferred option is an organic electroluminescent device, characterized by coating one or more layers via a sublimation process. In this case, the coating is typically less than 10 nm in a vacuum sublimation system. -5 millibars, preferably less than 10 -6 Material is applied by vapor deposition at an initial pressure of millibars. Alternatively, the initial pressure can be even lower or higher, for example, less than 10. -7 millibar.

[0315] Organic electroluminescent devices are also preferred, characterized by coating one or more layers by an OVPD (organic vapor deposition) method or by means of carrier gas sublimation. In this case, at 10 -5 The material is applied at a pressure of millibar to 1 bar. A special case of this method is the OVJP (Organic Vapor Jetting) method, in which the material is applied directly through a nozzle and thus structured.

[0316] Another preferred embodiment is an organic electroluminescent device, characterized by producing one or more layers from a solution, for example by spin coating or by any printing method, such as screen printing, flexographic printing, offset printing, or nozzle printing, but more preferably by LITI (photoinduced thermal imaging, thermal transfer printing) or inkjet printing. For this purpose, a soluble compound is required, which is obtained, for example, through suitable substitution. In a preferred embodiment of the invention, a layer comprising the compound of the invention is applied from a solution.

[0317] The organic electroluminescent device can also be produced as a hybrid system by applying one or more layers from a solution and applying one or more other layers by vapor deposition. For example, a light-emitting layer comprising the metal complex of the present invention and a matrix material can be applied from a solution, and a hole-blocking layer and / or an electron transport layer can be applied thereon by vapor deposition under reduced pressure.

[0318] These methods are generally known to those skilled in the art and can be applied without difficulty by those skilled in the art to organic electroluminescent devices comprising compounds of formula (1) or the preferred embodiments detailed above.

[0319] The electronic devices of the present invention, particularly organic electroluminescent devices, possess one or more of the following remarkable advantages over the prior art:

[0320] 1. The metal complex of the present invention exhibits directional luminescence. This achieves higher quantum efficiency via improved coupling output of light from the component, and thus higher OLED efficiency. This also results in extended lifetime, as the OLED can be operated with lower current.

[0321] 2. The metal complexes of the present invention can be synthesized with very short reaction times and at relatively low reaction temperatures in very high yields and with very high purity.

[0322] 3. The metal complex of the present invention has excellent thermal stability.

[0323] 4. The metal complexes of the present invention do not exhibit thermal isomerization / electro-isomerization or electro-electro ...

[0324] 5. Some of the metal complexes of the present invention have very narrow emission spectra, which produce high color purity in emission, particularly desirable for display applications.

[0325] 6. Organic electroluminescent devices containing the metal complex of the present invention as luminescent materials have very good lifespan.

[0326] 7. Organic electroluminescent devices containing the metal complex of the present invention as luminescent materials have excellent efficiency.

[0327] These advantages are not accompanied by a deterioration in other electronic properties.

[0328] The present invention is described in detail through the following embodiments, but is not intended to limit the invention. Those skilled in the art will be able to use the details given to create other electronic devices based on the invention without inventive effort, and thus practice the invention throughout the claimed scope. Detailed Implementation

[0329] Example:

[0330] General methods for determining orbital energies and electronic states

[0331] The HOMO and LUMO energies, as well as the triplet and singlet energy levels of the material, were determined via quantum chemical calculations. For this purpose, the "Gaussian09 D.01 version" software package (Gaussian Corporation) was used in this application. To calculate the energy of the metal-free organic material (referred to as the "org." method), geometry optimization was first performed using the semi-empirical AM1 method (Gaussian input line "#AM1opt") with charge 0 and multiplicity 1. Subsequently, based on the optimized geometry, single-point energy calculations were performed for the electronic ground state and triplet energy levels. This was performed using the TDDFT (Time-Related Density Functional Theory) method B3PW91 with the 6-31G(d) basis set (Gaussian input line "#B3PW91 / 6-31G(d)td=(50-50,nstates=4)") (charge 0, multiplicity 1). For organometallic compounds (referred to as the "M-org." method), the geometry is optimized using the Hartley-Fock method and the LanL2MB basis set (Gaussian input line "#HF / LanL2MB opt") (charge 0, multiplicity 1). As described above, energy calculations are performed similarly to those for organic materials, except that the "LanL2DZ" basis set is used for metal atoms and the "6-31G(d)" basis set is used for ligands (Gaussian input line "#B3PW91 / gen pseudo=lanl2td=(50-50,nstates=4)"). Based on the energy calculations, the HOMO is obtained in Hartley units as the last orbital occupied by two electrons (αocc. eigenvalue) and the LUMO as the first unoccupied orbital (αvirt. eigenvalue), where HEh and LEh represent the HOMO energy (in Hartley units) and the LUMO energy (in Hartley units), respectively. This is used to determine the HOMO and LUMO values ​​(in electron volts), calibrated by cyclic voltammetry measurements as follows:

[0332] HOMO(eV)=(HEh*27.212)*0.8308-1.118

[0333] LUMO(eV)=(LEh*27.212)*1.0658-0.5049

[0334] These values ​​are considered to be the HOMO and LUMO of the material.

[0335] The triplet energy level T1 of a material is defined as the relative excitation energy (in eV) of the triplet state with the lowest energy discovered through quantum chemical energy calculations.

[0336] The singlet energy level S1 of a material is defined as the relative excitation energy (in eV) of a singlet state with the second lowest energy discovered through quantum chemical energy calculations.

[0337] The singlet state with the lowest energy is called S0.

[0338] The methods described herein are independent of the software package used and consistently produce the same results. Examples of commonly used programs for this purpose are "Gaussian09" (Gaussian Corporation) and Q-Chem 4.1 (Q-Chem Corporation). In this application, the energy is calculated using the software package "Gaussian09 D.01 version".

[0339] Unless otherwise stated, the following synthesis was carried out in a dry solvent under a protective atmosphere. The metal complexes were also treated in the dark or under yellow light. Solvents and reagents can be purchased from, for example, Sigma-Aldrich or ABCR. The corresponding numbers in square brackets, or the numbers cited for individual compounds, relate to the CAS numbers of the compounds as known from the literature.

[0340] A. Organic synthons

[0341] 1. Synthesizers LS obtained from the literature

[0342] The following synthons are obtained from the literature and used to prepare the compounds of this invention:

[0343]

[0344]

[0345]

[0346]

[0347] 2. Synthesis of iodides through iodination

[0348] Example S1:

[0349]

[0350] In the dark, 43.0 g (100 mmol) of bis(trifluoroacetoxy)iodobenzene [2712-78-9] was added to a solution of 22.0 g (100 mmol) LS1 in 1000 mL of chloroform, followed by 12.7 g (50 mmol) of iodine [7553-56-2], and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured onto 500 mL of saturated sodium thiosulfate solution with stirring, and stirred for another 10 minutes. The organic phase was removed and dried with magnesium sulfate. The desiccant was filtered off and the filtrate was concentrated to dryness. The residue was purified by rapid chromatography (CombiFlash Torrent, Axel Semrau). Yield: 7.6 g (22 mmol), 22%; Purity: 95% (via...). 1 H NMR).

[0351] The following compounds can be prepared in a similar manner:

[0352]

[0353] 3. Synthesis of borate esters via borylation

[0354] General method:

[0355] While stirring, add 100 mmol of monobromide / monoiodide or 50 mmol of dibromide / diiodide, or 105 mmol of... To a mixture of bis(pinacolyl)diborane [73183-34-3], 200 mmol of anhydrous potassium acetate [127-08-2], and 300 mL of diane, 2 mmol of tricyclohexylphosphine [2622-14-2] and 1 mmol of palladium(II) acetate [3375-31-3] were added, and the mixture was stirred at 100 °C for 16 hours. After cooling, the diane was substantially removed under reduced pressure. The residue was dissolved in 500 ml of toluene and washed three times with 300 ml of water, and once with 300 ml of saturated NaCl solution. The organic phase was then dried with magnesium sulfate. After the drying agent had been filtered through a diatomaceous earth bed in the form of a toluene slurry and the toluene had been removed under reduced pressure, the residue was recrystallized twice from ethyl acetate / methanol. Repeated recrystallization and subsequent sublimation resulted in a diboronate ester obtained in this manner with a purity of >99.9% (by HPLC) for use as a monomer in the preparation of oligomers or polymers.

[0356] Example S20:

[0357]

[0358] The following ingredients were used: 34.6 g (100 mmol) of S1, 26.6 g (105 mol) of bis(pinacol)diborane, 19.6 g (200 mmol) of potassium acetate, 561 mg (2 mmol) of tricyclohexylphosphine, and 225 mg (1 mmol) of palladium(II) acetate. Yield: 15.2 g (44 mmol), 44%; Purity: >99% (by 1H NMR).

[0359] The following compounds can be prepared in a similar manner:

[0360]

[0361]

[0362]

[0363]

[0364]

[0365] 4. Synthesis of bromide / iodide via Suzuki coupling

[0366] Example S100:

[0367]

[0368] 39.6g (100mmol) of LS4, 36.0g (100mmol) of S21, 63.7g (300mmol) of tripotassium phosphate [7778-53-2], 500ml of toluene, and 200ml of dimethyl sulfoxide were added. To a mixture of alkane and 500 ml of water, 1.83 g (6 mmol) of tri-o-tolylphosphine [6163-58-2] and 225 mg (1 mmol) of palladium(II) acetate [3975-31-3] were added, and the mixture was stirred thoroughly at 100 °C for 18 hours. After cooling, the precipitated solid (part of the biconjugate product) was filtered off. The organic phase of the mother liquor was separated, washed twice with 300 ml of water each time and once with 300 ml of saturated sodium chloride solution, and dried with magnesium sulfate. The residue obtained after desiccant removal via diatomaceous earth bed in the form of toluene slurry by suction filtration was purified by rapid chromatography (CombiFlash Torrent, Axel Semrau). Yield: 27.8 g (48 mmol), 48%; Purity: 97% (by HPLC).

[0369] The following compounds can be prepared in a similar manner:

[0370]

[0371]

[0372]

[0373] 5. Boron esters synthesized via Suzuki coupling:

[0374] Example S200:

[0375]

[0376] To a mixture of 47.2 g (100 mmol) of S24, 57.9 g (100 mmol) of S100, 23.0 g (100 mmol) of tripotassium phosphate monohydrate [27176-10-9], and 500 mL of DMSO, 1.16 g (1 mmol) of tetrakis(triphenylphosphine)palladium(0) [14221-01-3] was added, and the mixture was stirred thoroughly at 80 °C for 18 hours. After cooling, the DMSO was substantially removed under reduced pressure, and the residue was dissolved in 1000 mL of hot toluene, filtered through a silica gel bed as a hot toluene slurry, and thoroughly washed with 500 mL of hot toluene. The organic phase was then concentrated to dryness under reduced pressure. The residue was boiled with 500 mL of isopropanol. After the crude product had been filtered off by suction and dried under reduced pressure, it was purified by rapid chromatography (CombiFlash Torrent, Axel Semrau). Yield: 22.3 g (28 mmol), 28%; Purity: approximately 97% (via 1 H NMR).

[0377] The following compounds can be prepared in a similar manner:

[0378]

[0379]

[0380] 6. Synthesis of hexadentate ligand 1:

[0381] Example L1:

[0382]

[0383] A mixture of 54.1 g (100 mmol) of 1,3,5-tris(2-bromophenyl)benzene [380626-56-2], 98.4 g (350 mmol) of 2-phenyl-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborphane-2-yl)pyridine [879291-27-7], 106.0 g (1 mol) of sodium carbonate, 5.8 g (5 mmol) of tetra(triphenylphosphine)palladium(0), 750 ml of toluene, 200 ml of ethanol, and 500 ml of water was heated under reflux with very good stirring for 24 hours. After 24 hours, 300 ml of 5% (w / w) aqueous solution of acetylcysteine ​​was added, and the mixture was stirred under reflux for another 16 hours and cooled. The aqueous phase was removed, and the organic phase was concentrated to dryness. After concentrating the organic phase from the Suzuki coupling, the brown foamy substance was dissolved in 300 ml of a dichloromethane:ethyl acetate mixture (8:1, v / v) and filtered through a silica gel bed as a dichloromethane:ethyl acetate slurry (8:1, v / v) (15 cm diameter, 20 cm length) to remove the brown component. Following concentration, the remaining foamy substance was recrystallized from 800 ml of ethyl acetate with the addition of 400 ml of methanol at boiling point, then recrystallized a second time from 1000 ml of pure ethyl acetate, and then sublimated under high vacuum by Kugelrohr (pressure: approx. 10⁻⁵ mbar, temperature: 280 °C). Yield: 50.6 g (66 mmol), 66%. Purity: approx. 99.7% (via...). 1 H NMR).

[0384] Example L2:

[0385]

[0386] Ligand L2 can be prepared in a similar manner. Instead of using 2-phenyl-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborhecyclopentan-2-yl)pyridine [879291-27-7], 2-[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborhecyclopentan-2-yl)phenyl]pyridine [908350-80-1]. Yield: 56.0 g (73 mmol), 73%. Purity: approximately 99.7% (by 1H NMR).

[0387] Example L3:

[0388]

[0389] L3 intermediate 1:

[0390]

[0391] A mixture of 22.6 g (100 mmol) of (6-methoxy-[1,1'-biphenyl]-3-yl)boronic acid [459423-16-6], 16.6 g (105 mmol) of 2-bromopyridine [109-04-6], 21.2 g (200 mmol) of sodium carbonate, 1.2 g (1 mmol) of tetrakis(triphenylphosphine)palladium [14221-01-3], 300 ml of toluene, 100 ml of ethanol, and 300 ml of water was heated under reflux with good stirring for 18 hours. After cooling, the organic phase was removed, washed twice with 300 ml of water and once with 300 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The oil obtained after concentrating the organic phase was dried at 80 °C under vacuum using an oil pump and then converted without further purification. Yield: 25.6 g (98 mmol), 98%; Purity: approximately 95% (via 1 H NMR).

[0392] L3 intermediate 2:

[0393]

[0394] 26.1 g (100 mmol) of L3 intermediate 1 and 81.9 g (700 mmol) of pyridine hydrochloride were mixed. The mixture was heated to 190°C for 3 hours. After cooling, the reaction mixture was poured into 500 mL of water and extracted five times with 200 mL of dichloromethane each time. The organic phase was washed twice with 200 mL of water and once with 200 mL of saturated NaCl solution. The solvent was removed under reduced pressure, and 300 mL of toluene was added for azeotropic drying, which was then completely distilled off under reduced pressure. The resulting viscous oily substance was converted without further purification. Yield: 21.0 g (85 mmol), 85%; Purity: approximately 95% (by 1H NMR).

[0395] L3 intermediate 3:

[0396]

[0397] Under good stirring, 34 mL (200 mmol) of trifluoromethanesulfonic anhydride [358-23-6] was added dropwise to a solution of 24.7 g (100 mmol) of L3 intermediate 2 cooled to 0 °C in a mixture of 300 mL dichloromethane and 80 mL pyridine. The reaction mixture was heated to room temperature and stirred for 16 hours, then poured into 1000 mL of ice water with stirring, and extracted three times with 300 mL of dichloromethane each time. The combined organic phases were washed twice with 300 mL of ice water each time and once with 500 mL of saturated NaCl solution, and then dried over sodium sulfate. The waxy residue remaining after removing dichloromethane under reduced pressure was recrystallized from acetonitrile. Yield: 32.6 g (86 mmol), 86%; Purity: approximately 95% (via 1 H NMR).

[0398] L3 intermediate 4:

[0399]

[0400] While stirring, 37.9 g (100 mmol) of L3 intermediate 3 and 2.2 g (3 mmol) of (DPPF)PdCl2 were added to 250 ml of dimethyl ether. In a solution of alkane, 41.6 ml (300 mmol) of triethylamine was added, followed by 29.0 ml (200 mmol) of 4,4,5,5-tetramethyl-[1,3,2]dioxaboronium cyclopentane [25015-63-8]. The mixture was then heated under reflux for 18 hours. After cooling, the solvent was substantially removed under reduced pressure, and the residue was dissolved in 300 ml of ethyl acetate, washed three times with 100 ml of water each time, and once with 200 ml of saturated sodium chloride solution, and dried over magnesium sulfate. After filtering out the drying agent, the solvent was removed under reduced pressure. The resulting oily residue was further converted without purification. Yield: 33.9 g (95 mmol), 95%; Purity: approximately 95% (via 1 H NMR).

[0401] L3 intermediate 5:

[0402]

[0403] A mixture of 35.7 g (100 mmol) of L3 intermediate 4, 28.3 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, 100 ml of ethanol, and 300 ml of water was heated under reflux for 48 hours. After cooling, the organic phase was removed, and the mixture was washed three times with 100 ml of water and once with 100 ml of saturated sodium chloride solution, and dried with magnesium sulfate. The desiccant was filtered through a diatomaceous earth bed as a toluene slurry, toluene was removed under reduced pressure, and excess 1-bromo-2-iodobenzene was removed under reduced pressure (approximately 0.1 mbar) at 80 °C.

[0404] Yield: 36.7 g (95 mmol), 95%; Purity: approximately 95% (via 1 H NMR).

[0405] L3:

[0406] 66.3 g (100 mmol) of 2-[4-[2-[3-[2-[4-(2-pyridyl)phenyl]phenyl]-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentan-2-yl)phenyl]phenyl]phenyl]pyridine [1989597-72-9], 38.6 g (100 mmol) of L3 intermediate 5, 63.7 g (300 mmol) of tripotassium phosphate, 1.6 g (4 mmol) of SPhos, 449 mg (2 mmol) of palladium(II) acetate, 500 ml of toluene, and 250 ml of dioxin were added. A mixture of alkane and 500 ml of water was heated under reflux for 18 hours. After cooling, the organic phase was separated, washed three times with 200 ml of water each time and once with 200 ml of saturated sodium chloride solution, and dried with magnesium sulfate. The drying agent was filtered off using a diatomaceous earth bed in the form of toluene slurry. The solvent was removed under reduced pressure, and the residue was recrystallized from 300 ml of acetonitrile by adding approximately 80 ml of ethyl acetate while boiling. Yield: 69.9 g (83 mmol), 83%; Purity: approximately 95% (via 1 H NMR).

[0407] Example L4:

[0408]

[0409] L4 can be obtained similarly to L3, except that 2-bromo-4-tert-butylpyridine [50488-34-1] is used instead of 2-bromopyridine.

[0410] Example L5:

[0411]

[0412] L5 can be obtained similarly to L3, except that 4-tert-butyl-2-[4-[2-[3-[2-[4-(4-tert-butyl-2-pyridyl)phenyl]phenyl]-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentan-2-yl)phenyl]phenyl]phenyl]pyridine [1989597-75-2] is used instead of 2-[4-[2-[3-[2-[4-(2-pyridyl)phenyl]phenyl]-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentan-2-yl)phenyl]phenyl]phenyl]pyridine [1989597-72-9].

[0413] B: Organometallic synthons

[0414] 1. Metal complex synthons MS obtained from the literature:

[0415]

[0416]

[0417]

[0418]

[0419] 2. Synthesis of the metal complex Ir(L1):

[0420] Example Ir(L1):

[0421]

[0422] Initially, a mixture of 7.66 g (10 mmol) of ligand L1, 4.90 g (10 mmol) of iridium(III) triacetylacetone [15635-87-7], and 120 g of hydroquinone [123-31-9] was added to a 500 ml double-necked round-bottom flask with a glass-coated magnetic core. The flask was equipped with a water separator (for media with a density less than water), an air condenser, and argon protection. The flask was placed in a metal heating bath. The apparatus was purged with argon from the top via the argon protection system for 15 minutes, allowing argon to escape from the side neck of the double-necked flask. A glass-coated Pt-100 thermocouple was introduced into the flask via the side neck, with its end positioned directly above the magnetic stirrer core. The apparatus was then insulated with several loose turns of household aluminum foil, which extended upwards to the middle of the riser tube of the water separator. The apparatus was then rapidly heated to 250°C–260°C using a heated laboratory stirrer system, measured with a Pt-100 thermal sensor immersed in the molten, stirred reaction mixture. The reaction mixture was maintained at 250°C–260°C for the following 1.5 hours, during which a small amount of condensate was distilled off and collected in a water separator. After cooling, the melt cake was mechanically pulverized and extracted by boiling in 500 ml of methanol. The resulting beige suspension was filtered through a double-ended glass frit filter, and the beige solid was washed once with 50 ml of methanol and then dried under reduced pressure. Crude yield: quantitative. The resulting solid was dissolved in 1500 ml of dichloromethane and filtered in the dark, under air-free conditions, as a dichloromethane slurry (column diameter: approximately 18 cm), leaving a dark component initially. The core fraction was cut off and substantially concentrated on a rotary evaporator while MeOH was continuously added dropwise until crystallization. After removal by suction, washing with a small amount of MeOH, and drying under reduced pressure, the yellow product was further purified by three consecutive hot extractions with toluene / acetonitrile (3:1, v / v) and five hot extractions with toluene (initially about 150 ml in each case; extraction sleeve: standard Soxhlet sleeve made of cellulose from Whatman). Yield: 8.52 g (8.9 mmol), 89%. Purity: >99.9% (by HPLC).

[0423] Example Ir(L2):

[0424]

[0425] Similarly, Ir(L2) can be prepared using L2 instead of L1. Purification was achieved by recrystallization three times from NMP with methanol added while the solution was cooled. Yield: 8.04 g (8.4 mmol), 84%. Purity: >99.7% (by HPLC).

[0426] In a similar manner, the following metal complexes can be prepared, purified as described for Ir(L1).

[0427]

[0428]

[0429] 3. Halogenation of metal complexes Ir(L1):

[0430] General procedure:

[0431] In the dark and under ventilated conditions, at -30°C to +30°C, add 10.5 mmol of N-halosuccinimide (halogens: Cl, Br, I; A = 1 corresponds to a monohalogenation, A = 2 to a dihalogenation, and A = 3 to a trihalogenation) to a solution or suspension of 10 mmol of the complex with an A×CH group at the para position of the iridium in 500 ml to 2000 ml of DCM (dichloromethane) (depending on the solubility of the metal complex), and stir the mixture for 20 hours. The slightly soluble complex in DCM can also be converted in other solvents (TCE, THF, DMF, chlorobenzene, etc.) at elevated temperatures. Subsequently, the solvent is substantially removed under reduced pressure. The residue is extracted by boiling with 100 ml of methanol, and the solid is filtered off by suction, washed three times with about 30 ml of methanol, and then dried under reduced pressure. Substoichiometric bromination of complexes with three CH groups at the para position of iridium, such as monobromination and dibromination, is typically carried out with less selectivity than stoichiometric bromination. The crude products of these brominations can be separated by chromatography (CombiFlash Torrent, from A. Semrau).

[0432] Example Ir(L1-3Br):

[0433]

[0434] 5.6 g (31.5 mmol) of N-bromosuccinimide was added in a single addition to a suspension of 9.6 g (10 mmol) of Ir(L1) in 2000 ml of DCM, which was stirred at 0 °C. The mixture was then stirred for another 20 hours. After removing approximately 1900 ml of DCM under reduced pressure, 100 ml of methanol was added to the yellow suspension, which was then boiled with stirring. The solid was filtered off by suction, washed three times with approximately 30 ml of methanol, and then dried under reduced pressure. Yield: 11.3 g (9.5 mmol), 95%; Purity: >99.0% (by NMR).

[0435] In a similar manner, the following complexes can be prepared:

[0436]

[0437]

[0438]

[0439] 4. Preparation of the metal complex of the present invention

[0440] Variant 1: Suzuki Coupling in Two-Phase Aqueous Organic Media

[0441] To 10 mmol of brominated metal complex, A×11 mmol of monoboronate (where for monobromide, dibromide) A mixture of tribromide or tribromide (A = 1, 2, or 3), A × 30 mmol of tripotassium phosphate [7778-53-2], 300 ml of toluene, 100 ml of diane, and 100 ml of water was added, along with A × 0.6 mmol of tri-o-tolylphosphine [6163-58-2] and A × 0.1 mmol of palladium(II) acetate [3975-31-3]. The mixture was stirred thoroughly at 100 °C for 18 hours. After cooling, the precipitated solid was filtered off by suction. If no solid precipitate was formed, the organic phase was removed, washed twice with 300 ml of water and once with 300 ml of saturated sodium chloride solution, dried over magnesium sulfate, filtered off the magnesium sulfate, and the filtrate was concentrated to dryness. The crude product obtained was purified by chromatography or rapid chromatography (CombiFlash Torrent, from Axel Semirau). Further purification is achieved by repeated continuous thermal extraction, wherein the product is introduced into a cellulose sleeve (from Waterman) in a thermal extractor and repeatedly thermally extracted (usually 3 to 6 times) with a suitable thermal extractant, such as toluene, chlorobenzene, anisole, ethyl acetate, butyl acetate, acetonitrile, dichloromethane, etc. (initially about 150 ml to 200 ml) until a purity >99.5%, preferably >99.9%, is achieved.

[0442] Variant 2: Suzuki Coupling in Single-Phase Dipole Nonproton Medium

[0443] To a mixture of 10 mmol of the metal complex, A × 11 mmol of monoboronate (where A = 1, 2, or 3 for monobromide, dibromide, or tribromide), A × 30 mmol of tripotassium phosphate trihydrate [22763-03-7], and 200 ml of DMSO, A × 0.1 mmol of tetrakis(triphenylphosphine)palladium(0) [14221-01-3] was added, and the mixture was stirred thoroughly at 80 °C for 18 hours. After cooling, the DMSO was substantially removed under reduced pressure, the residue was dissolved in 1000 ml of dichloromethane and filtered through a silica gel bed as a dichloromethane slurry, the bed was thoroughly washed with 500 ml of dichloromethane, and the organic phase was concentrated to dryness under reduced pressure. The crude product thus obtained was further purified as described in variant 1 below.

[0444] Example Ir1: MS1 + 3 × S20 → (MS1 - 3 × S20) = Ir1

[0445]

[0446] According to the procedure of variant 1. Using 8.92 g (10.0 mmol) MS1, 11.43 g (33.0 mmol) S20, 19.12 g (90.0 mmol) tripotassium phosphate, 548 mg (1.8 mmol) tri-o-tolylphosphine, and 67 mg (0.3 mmol) palladium(II) acetate. Thermal extraction: carried out 5 times from toluene. Yield: (4.8 mmol), 48%. Purity: >99.8% (by HPLC).

[0447] The following compounds can be prepared in a similar manner:

[0448]

[0449]

[0450]

[0451]

[0452]

[0453]

[0454]

[0455] *: If different from Example Ir1

[0456] 5) Oligomeric / polymeric metal complexes

[0457] General polymerization methods for bromide or boric acid derivatives as polymerizable groups: Suzuki polymerization

[0458] Variant A: Biphasic reaction mixture

[0459] The procedure was performed according to WO 2002 / 077060 and WO 2003 / 048225, under inert conditions using a carefully degassed solvent. The monomers (bromine and boric acid or boron) were... The esters (purity (by HPLC) >99.8%) were converted to a total concentration of approximately 100 mmol / L in a mixture of 3 parts by volume toluene: 6 parts by volume diane: 2 parts by volume water, as specified in the table below. Monomers M1 and M2 were always added completely initially. Then, 2 mol equivalents of tripotassium phosphate were added to each Br functional group used in the whole, the mixture was stirred for another 5 minutes, then 0.06 mol equivalents of tri-o-tolylphosphine were added to each Br functional group used, followed by 0.01 mol equivalents of palladium(II) acetate, and the mixture was heated under reflux with very good stirring. After 1 hour, the remaining monomers according to the table were added all at once, and the mixture was heated under reflux for another 4 hours. If the viscosity of the mixture increased too significantly, a mixture of 2 parts by volume toluene: 3 parts by volume diane was used. The mixture of alkanes was diluted. After a total reaction time of 4-6 hours, for end-capping, 0.05 mol equivalents of a monobromoaromatic compound (here, 3-bromobiphenyl [2113-57-7]) were added to each of the boronic acid functional groups used, followed by 0.05 mol equivalents of monoboronic acid or monoboronic ester (here, pinacol 3-biphenylboronic acid [912844-88-3]) to each of the Br functional groups used, and the mixture was boiled again for 1 hour. After cooling, the mixture was diluted with 500 ml of toluene, the aqueous phase was removed, and the organic phase was washed twice with 300 ml of water each time. The organic phase was stirred at 80 °C with 300 ml of 5% N-acetylcysteine ​​aqueous solution for 16 hours, and the organic phase was removed, dried with magnesium sulfate, filtered through a diatomaceous earth bed, and then concentrated to dryness. The crude polymer was dissolved in THF (concentration approximately 10 g / L–30 g / L), and the solution was gradually added to twice its volume of methanol under very good stirring. The polymer was filtered off by suction and washed three times with methanol and dried. The reprecipitation process was repeated five times, and the polymer was then dried under reduced pressure at 30–50 °C to constant weight.

[0460] Variant B: Single-phase reaction mixture

[0461] The monomers (bromine and boric acid or borate ester, purity (by HPLC) >99.8%) were dissolved or suspended in a solvent (THF, dimethyl methacrylate) at a total concentration of approximately 100 mmol / L according to the compositions specified in the table below. The mixture is prepared by adding 3 molar equivalents of a base (potassium fluoride, tripotassium phosphate (anhydrous, monohydrate, or trihydrate), potassium carbonate, cesium carbonate, etc., each in anhydrous form) and equivalent weights of glass beads (3 mm in diameter) to each Br functional group. The mixture is then stirred for another 5 minutes. Next, 0.03 to 0.003 molar equivalents of tri-o-tolylphosphine are added to each Br functional group, followed by 0.005 to 0.0005 molar equivalents of palladium(II) acetate (preferably, the phosphine to Pd ratio is 6:1). The mixture is then heated to 80°C and refluxed for 2-3 hours with very good stirring. Alternatively, other phosphines, such as tri-tert-butylphosphine, SPhos, XPhos, RuPhos, XanthPhos, etc., can be used. In the case of these phosphines, the preferred phosphine:palladium ratio is 2:1 to 1.3:1. After a total reaction time of 4 to 12 hours, 0.05 molar equivalents of a monobromoaromatic compound (see above) were added for end-capping, followed by 0.05 molar equivalents of monoboric acid or monoboric ester (see above) after 30 minutes. The mixture was then boiled for another hour. The solvent was substantially removed under reduced pressure, and the residue was dissolved in toluene and the polymer was purified as described in variant A.

[0462] Oligomers / polymers P consisting of monomers M1 to M5 and their composition, expressed in mmol:

[0463]

[0464] Stereochemistry:

[0465] Typically, the mononuclear complex synthesis unit is used in the form of racemic mixtures of the Δ and Λ isomers. This yields diastereomeric mixtures of the polynuclear compounds of the present invention, such as the Δ,Δ / Λ,Λ and (meta-)Δ,Λ forms of dinuclear compounds. Unless otherwise stated, these are further converted or used as diastereomeric mixtures. Furthermore, these can be separated by chromatography or by fractional crystallization.

[0466] Example: OLED Manufacturing

[0467] 1) Vacuum-processed devices:

[0468] The OLEDs of the present invention and those of the prior art are manufactured by means of the general method according to WO 04 / 058911, wherein the general method is adapted according to the circumstances described herein (the variations lie in the layer thickness and the materials used).

[0469] In the following embodiments, various OLED results are presented. A glass plate coated with a 50 nm thick structured ITO (indium tin oxide) forms the substrate for applying the OLED. The OLED essentially has the following layer structure: substrate / hole transport layer 1 (HTL) (which consists of HTN (commercially available from Novaled) doped with 5% NDP-9, 20 nm) / hole transport layer 2 (HTL2) / optional electron blocking layer (EBL) / light emitting layer (EML) / optional hole blocking layer (HBL) / electron transport layer (ETL) / optional electron injection layer (EIL) and finally the cathode. The cathode is formed of a 100 nm thick aluminum layer.

[0470] First, vacuum-processed OLEDs will be described. For this purpose, all materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the light-emitting layer always consists of at least one matrix material (host material) and light-emitting dopants (emitters) added to one or more matrix materials by co-evaporation in specific volume proportions. Details given in the form of M3:M2:Ir(L2) (55%:35%:10%) mean that material M3 is present in the layer at a volume proportion of 55%, M2 at a volume proportion of 35%, and Ir(L2) at a proportion of 10%. In a similar manner, the electron transport layer can also be composed of a mixture of the two materials. The exact structure of the OLED can be seen in Table 1. The materials used to produce the OLED are shown in Table 4.

[0471] OLEDs are characterized using standard methods. For this purpose, the electroluminescence spectrum is determined, and the current efficiency (measured in cd / A) and voltage (measured in 1000 cd / m²) are determined from the current-voltage-luminance characteristic line (IUL characteristic line). For the selected experiments, lifetime is determined. Lifetime is defined as the time it takes for the luminance to decrease from a specific initial luminance to a certain percentage. Lifetime LD50 means that the lifetime is the time it takes for the luminance to decrease to 50% of the initial luminance, i.e., from, for example, 1000 cd / m² to 500 cd / m². Different initial luminances are selected based on the emitted color. Lifetime values ​​can be converted to values ​​for other initial luminances using conversion formulas known to those skilled in the art. In this context, lifetime values ​​for an initial luminance of 1000 cd / m² are commonly used.

[0472] Use of the compounds of the present invention as light-emitting materials in phosphorescent OLEDs

[0473] The compounds of this invention are particularly useful as phosphorescent materials in the emissive layer of OLEDs. A comparison using prior art is made based on the iridium compounds in Table 4. Results for OLEDs are summarized in Table 2.

[0474] Table 1: Structure of OLED

[0475]

[0476] Table 2: Results of Vacuum Processing of OLEDs

[0477]

[0478] Solution processing devices

[0479] A: Made from low molecular weight soluble functional materials

[0480] The iridium complexes of this invention can also be processed from solution to produce OLEDs, which are significantly simpler to manufacture than vacuum-processed OLEDs, yet still possess very good properties. The fabrication of these components is based on the fabrication of polymer light-emitting diodes (PLEDs), which has been described multiple times in the literature (e.g., in WO 2004 / 037887). The structure consists of a substrate / ITO / hole injection layer (60 nm) / intermediate layer (20 nm) / light-emitting layer (60 nm) / hole blocking layer (10 nm) / electron transport layer (40 nm) / cathode. For this purpose, a substrate (soda-lime glass) from Technoprint is used, on which an ITO structure (indium tin oxide, transparent conductive anode) is applied. The substrate is cleaned in a clean chamber with deionized water and detergent (Deconex 15PF), and then activated by UV / ozone plasma treatment. Subsequently, also in a clean chamber, a 20 nm hole injection layer is applied by spin coating. The required spin rate depends on the dilution and the specific spin coater geometry. To remove residual water from the layer, the substrate is baked on a hot plate at 200°C for 30 minutes. The intermediate layer used is for hole transport; in this case, HL-X092 from Merck is used. The intermediate layer can optionally be replaced by one or more layers, provided that it does not leach out again due to subsequent processing steps involving EML deposition from the solution. To produce the luminescent layer, the triplet luminescent material of the present invention is dissolved together with the matrix material in toluene or chlorobenzene. If, as here, the device is to achieve a typical layer thickness of 60 nm by spin coating, then the typical solids content of these solutions is 16 g / L to 25 g / L. The solution-processed Type 1a device contains a light-emitting layer composed of M4:M5:IrL (42%:45%:13%), the Type 1b device contains a light-emitting layer composed of M4:M5:IrL (40%:32%:28%), and the Type 2 device contains a light-emitting layer composed of M4:M5:IrLa:IrLb (30%:35%:30%:5%), meaning they contain two different Ir complexes. The light-emitting layers were spin-coated in an inert atmosphere (argon in this application) and baked at 160°C for 10 minutes. A hole-blocking layer (10 nm ETM1) and an electron transport layer (40 nm ETM1 (50%) / ETM2 (50%)) were vapor-deposited on top of the latter (from Lesker's vapor deposition system, typical vapor deposition pressure: 5 × 10⁻⁶ mbar). Finally, an aluminum cathode (100 nm) (high-purity metal from Aldrich) was applied via vapor deposition. To protect the device from air and humidity, it was ultimately encapsulated and then characterized. The cited OLED embodiments have not been optimized. Table 3 summarizes the obtained data.

[0481] Table 3: Results of material treatment from solution

[0482]

[0483]

[0484] Table 4: Structural Formulas of the Materials Used

[0485]

[0486]

[0487]

Claims

1. A compound of formula (1) Equation (1) The symbols and markings used are as follows: M is an organometallic iridium complex containing three bidentate monoanion ligands or one tripod hexadentate trianion ligand; The tripod hexadentate trianion ligand contains three bidentate monoanion subligands, which are either the same or different in each case and are selected from the structures of formulas (L-1) and (L-2): The dashed bond represents the bond between the subligand and the bridging group, wherein the bridging group in the tripod hexadecanoid trianion ligand is a group of formula (6) or formula (10). Equation (6) Equation (10) The dashed bonds represent the bonds between the bidentate subligands and this structure; and A is either the same or different in each case, and is a group of -CR2-CR2- or the following formula (15): The dashed lines indicate the positions of the bonds between the bidentate subligands and this structure, and This indicates the position where the unit of formula (15) is connected to the central cyclic group in formula (6) or formula (10); A 1 It is the same or different in each case, and it is CR2; Furthermore, the bidentate monoanion ligand is selected from the structure of formula (L-1'): The symbols used are as follows: CyC is the same or different in each case, and is a group of formula (CyC-1a), which is coordinated with a metal via a carbon atom and covalently bonded to CyD; This group is bonded to CyD at the position indicated by # and is also... The indicated location is coordinated with the metal; The condition is that when the bridging group of formula (6) or (10) is bonded to CyC, the substituent R labeled with o is absent and the bridging group of formula (6) or (10) is bonded to this carbon atom; Additionally, the condition is that when the Ar group is bonded to CyC, a substituent R is absent and the Ar group is bonded to this carbon atom; CyD is the same or different in each case, and is a group of formula (CyD-1a) or (CyD-2a), which is covalently bonded to CyC. This group is bonded to CyC at the position indicated by # and is also... The indicated location is coordinated with the metal; The condition is that when the bridging group of formula (6) or (10) is bonded to CyD, the substituent R labeled with o is absent and the bridging group of formula (6) or (10) is bonded to this carbon atom; Additionally, the condition is that when the Ar group is bonded to CyD, a substituent R is absent and the Ar group is bonded to this carbon atom; Ar is either the same or different in each case, and Ar is selected from groups of formula (Ar-1) to (Ar-10): The dashed bond indicates the connection of such groups, where X is the same or different in each case and is CR; W is the same or different in each case and is NR, O, or S; B is a group of formula (2) below: Equation (2) The dashed bond indicates that this group is related to Ar or R. B The connection, and in addition: Y 1 Y 2 Y 3 In each case, it may be the same or different, and is a CR2, CR2-CR2, CR2-CR2-CR2, CR2-CR2-CR2-CR2, CR=CR, or ortho-bonded phenylene group, wherein the phenylene group may be substituted by one or more R groups; meanwhile, the Y 1 Y 2 and / or Y 3 Groups can be linked together by single bonds or via R groups to form oligocyclic ring groups; R B In each case, the alkyl group may be the same or different, and is selected from M or H, D, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl group in each case may be one or more R 1 Group substitution, or an aromatic ring system or heteroaromatic ring system having 6 to 24 aromatic ring atoms and in each case being substituted by one or more R groups. 1 Group substitution; R is the same or different in each case, and is H, D, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or an aromatic ring system or heteroaromatic ring system having 6 aromatic ring atoms and in each case can be one or more R. 1 Group substitution; at the same time, two R groups can also form a ring system together; R 1 In each case, it may be the same or different, and is H, D, a straight-chain alkyl group having 1 to 5 carbon atoms or a branched or cyclic alkyl group having 3 to 5 carbon atoms, wherein the alkyl group in each case may be one or more R 2 Group substitution, or an aromatic ring system or heteroaromatic ring system having 6 aromatic ring atoms and in each case being substituted by one or more R groups. 2 Group substitution; simultaneously, two or more R groups 1 Groups can form ring systems together; R 2 In each case, it may be the same or different, and it is H, D, or an aliphatic hydrocarbon group having 1 to 5 carbon atoms; n is 1, 2, or 3; p is the same or different in each case, and is between 1 and 10; q is the same or different in each case, and is between 0 and 10; m is the same or different in each case, and is between 1 and 10, and The following compounds were excluded. 。 2. The compound according to claim 1, characterized in that... The triplet energy of fragment M at q=0 is lower than that of fragment -[[Ar] p -B] m -R B The triplet energy may be higher than that of the fragment -[[Ar] when q=1 to 10. p -B-[Ar] p ] m -R B The triplet energy does not exceed 0.1 eV.

3. The compound according to claim 1 or 2, characterized in that... The Y 1 Y 2 and Y 3 The groups are the same and are CH2, CH2-CH2, CH2-CH2-CH2, CH2-CH2-CH2-CH2 or unsubstituted o-phenylene groups.

4. The compound according to claim 1 or 2, characterized in that... The groups in formula (2) are selected from structures (B-1) to (B-6). The dashed bond in each case represents the connection of this group.

5. The compound according to claim 1 or 2, characterized in that... R B Selected from H, M, straight-chain alkyl groups having 1 to 10 carbon atoms or branched or cyclic alkyl groups having 3 to 10 carbon atoms, wherein the alkyl group in each case can be generated by one or more R 1 Group substitution, or an aromatic ring system or heteroaromatic ring system having 6 to 24 aromatic ring atoms and in each case being substituted by one or more R groups. 1 Group substitution.

6. An oligomer, polymer, or dendritic macromolecule containing one or more compounds according to any one of claims 1 to 5, wherein one or more of the compounds are present in combination with the polymer, oligomer, or dendritic macromolecule.

7. A formulation comprising at least one compound according to any one of claims 1 to 5 or an oligomer, polymer or dendritic macromolecule according to claim 6 and at least one other compound.

8. Use of the compound according to any one of claims 1 to 5 or the oligomer, polymer or dendritic macromolecule according to claim 6 in electronic devices.

9. An electronic device selected from organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic optical detectors, organic photosensors, organic field quenching devices, light-emitting electrochemical cells, and organic laser diodes, wherein the electronic device comprises at least one compound according to any one of claims 1 to 5 or at least one oligomer, polymer, or dendritic macromolecule according to claim 6.

10. The electronic device according to claim 9, wherein the electronic device is an organic electroluminescent device, characterized in that... The compound according to any one of claims 1 to 5 is used as a luminescent compound in one or more luminescent layers.

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