Bimetallic complexes and electronic devices, in particular organic electroluminescent devices, containing said metal complexes

Abstract

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

Description

Technical Field

[0001] This invention relates to binuclear metal complexes, which are suitable for use as light emitters in organic electroluminescent devices. Background Technology

[0002] According to existing technology, triplet emitters used in phosphorescent organic light-emitting devices (OLEDs) are particularly iridium complexes with bi-ortho and tri-ortho metallization and 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 such complexes are tris(phenylpyridyl)iridium(III) and its derivatives, where the ligands used are, for example, 1-phenylisoquinoline or 3-phenylisoquinoline, 2-phenylquinoline or phenylcarbene. In this case, these iridium complexes typically have considerably long emission lifetimes, significantly greater than 1 μs. However, for use in OLEDs, short emission lifetimes are required to enable operation of OLEDs with high brightness and low roll-off characteristics. Improvements in the efficiency of red phosphorescent emitters are also needed. Due to the low triplet energy level T1 in the case of conventional red phosphorescent emitters, the photoluminescence quantum yield is typically much lower than theoretically possible, because at low T1, the non-radiative channel also plays a significant role, especially when the complex has a high emission lifetime. This needs to be improved by increasing the radiation level, which in turn can be achieved by reducing the photoluminescence lifetime.

[0003] Improvements in complex stability have been achieved through the use of multi-legged ligands, as described, for example, in WO 2004 / 081017, US 7,332,232, and WO 2016 / 124304. Even though these complexes show advantages over complexes with the same ligand structure but where individual ligands lack multi-legged bridging, further improvements are still needed. Therefore, even with complexes containing multi-legged ligands, improvements are still required in terms of performance, particularly in terms of excited-state emission lifetime, efficiency, voltage, and / or lifetime, when used in organic electroluminescent devices.

[0004] US 2003 / 0152802 discloses bimetallic iridium complexes having bridging ligands that coordinate with two metals. These complexes are synthesized in multiple stages, which constitutes a disadvantage in the synthesis. Furthermore, planar-mesomeric isomerization and ligand perturbation may occur in these complexes, which are also detrimental. Summary of the Invention

[0005] Therefore, one object of the present invention is to provide novel metal complexes suitable for use as light emitters in OLEDs. A specific object is to provide light emitters exhibiting improved performance in terms of efficiency, operating voltage, and / or lifetime.

[0006] Surprisingly, the dinuclear rhodium and iridium complexes described below exhibit significantly improved photophysical properties compared to their corresponding mononuclear complexes, and thus lead to improved performance when used in organic electroluminescent devices. More specifically, the compounds of the present invention possess improved photoluminescence quantum yield and significantly reduced luminescence lifetime. The shorter luminescence lifetime results in improved roll-off characteristics of organic electroluminescent devices. The present invention provides these complexes and organic electroluminescent devices comprising these complexes.

[0007] Therefore, the present invention provides a compound of the following formula (1):

[0008]

[0009] The symbols used are as follows:

[0010] M may be the same or different in each case and is either iridium or rhodium;

[0011] D is the same or different in each case and is C or N, provided that a C and an N are coordinated with each of the two M;

[0012] X is the same or different in each case and is CR or N;

[0013] V is the same or different in each case and is a group of the following formula (2) or (3):

[0014]

[0015] One of the dashed bonds represents a bond connected to the corresponding six-membered aryl or heteroaryl group shown in formula (1), and the other two dashed bonds each represent a bond connected to the subligand L.

[0016] L is the same or different in each case and is a bidentate monoanion subligand;

[0017] X 1 In each case, they may be the same or different, and it is CR or N;

[0018] A 1 In each case, they may be the same or different and are either C(R)2 or O;

[0019] A 2 In each case, the same or different and is CR, P (=O), B, or SiR, the condition is that when A 2 When =P (=O), B, or SiR, the symbol A 1 It is O and with the A 2 The bond symbol A is neither -C(=O)-NR'- nor -C(=O)-O-;

[0020] A is the same or different in each case and is a group of –CR=CR-, -C(=O)-NR'-, -C(=O)-O-, -CR2-CR2-, -CR2-O- or the following formula (4):

[0021]

[0022] The dashed bond represents the bonding position of the bidentate subligand L or the corresponding six-membered aryl or heteroaryl group depicted in formula (1) with the structure, and * represents the connection position of the unit and the central cyclic group of formula (4), i.e. the group explicitly shown in formula (2) or (3).

[0023] X 2 In each case, they are 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, the same or different and is CR or N; or when X in the ring 3 When one of the groups is N, two adjacent X 2 The groups together are either CR or N, thus forming a five-membered ring; the condition is that there are no more than two adjacent X groups. 2 The group is N;

[0024] X 3 In each case, it is C, or an X in the same ring. 3 The group is N and the other is X 3 The group is C; the condition is that when X in the ring 3 When one of the groups is N, two adjacent X 2 The groups together are CR or N;

[0025] 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 1 COO (cation), SO3 (cation), OSO3 (cation), OPO3 (cation)2, O (cation), N (R) 1 )3 (anion), P(R) 1)3 (anion), a straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or alkynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or alkynyl group in each case may be one or more R 1 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by Si(R) 1 2. C=O, NR 1 O, S or CONR 1 Instead, or having 5 to 40 aromatic ring atoms and in each case being one or more R 1 Aromatic or heteroaromatic ring systems with substituted groups; at the same time, two R groups together can also form a ring system;

[0026] 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 may be replaced by Si(R) 1 )2 is replaced, or has 5 to 40 aromatic ring atoms and in each case can be replaced by one or more R 1 Aromatic or heteroaromatic ring systems with substituted groups;

[0027] R 1 The same or different in each case 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 COO (cation), SO3 (cation), OSO3 (cation), OPO3 (cation)2, O (cation), N (R) 2 )3 (anion), P(R) 2 )3 (anion), a straight-chain alkyl group having 1 to 20 carbon atoms, or an alkenyl or alkynyl group having 2 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, wherein the alkyl, alkenyl, or alkynyl group in each case may be one or more R 2 Group substitution, wherein one or more non-adjacent CH2 groups can be replaced by Si(R) 22. C=O, NR 2 O, S or CONR 2 Instead, or having 5 to 40 aromatic ring atoms and in each case being one or more R 2 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two or more R groups... 1 Groups together can form a ring system;

[0028] R 2 In each case, 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, wherein one or more hydrogen atoms may be replaced by F;

[0029] The cations may be the same or different in each case and are selected from protons, deuterons, alkali metal ions, alkaline earth metal ions, ammonium, tetraalkylammonium, and tetraalkyl.

[0030] The anion may be the same or different in each case and is selected from halide ions, carboxylate ions, and R. 2 -COO - Cyanide ion, cyanate ion, isocyanate ion, thiocyanate ion, isothiocyanate ion, hydroxide ion, BF4 - PF6 - B(C6F5)4 - carbonate ions and sulfonate ions.

[0031] When two R or R 1 When groups together form a ring system, it can be monocyclic or polycyclic and can be 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 further apart from each other.

[0032] In the context of this specification, the phrase "two or more groups together can form a ring" specifically refers to two groups bonded together by chemical bonds and formally eliminating two hydrogen atoms. This is illustrated by the following scheme:

[0033]

[0034] However, the above wording also means that if one of the two groups is hydrogen, the second group binds to the bonding position of the hydrogen atom, thereby forming a ring. This will be illustrated by the following scheme:

[0035]

[0036] The formation of the aromatic ring system will be explained through the following scheme:

[0037]

[0038] Such cyclization can occur in groups bonded to carbon atoms that are directly bonded to each other, or in groups bonded to carbon atoms that are further apart. Preferably, such cyclization occurs in groups bonded to carbon atoms that are directly bonded to each other or in groups bonded to the same carbon atom.

[0039] In the context of this invention, an aryl group contains 6 to 40 carbon atoms; a heteroaryl group in the context of this invention contains 2 to 40 carbon atoms and at least one heteroatom, provided that the sum of the carbon atoms and the heteroatom is at least 5. The heteroatom is preferably selected from N, O, and / or S. An aryl group or heteroaryl group herein refers to 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.

[0040] 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 or heteroaromatic ring system refers to a system that does not necessarily contain only aryl or heteroaromatic groups, but in which multiple aryl or heteroaromatic groups may also be interrupted by non-aromatic units (preferably less than 10% of non-H atoms), such as carbon, nitrogen, or oxygen atoms or carbonyl groups. For example, systems such as 9,9'-spirodifluorene, 9,9'-diarylfluorene, triarylamines, diaryl ethers, piracene, etc., should therefore also be considered aromatic ring systems in the context of this invention, as should systems in which two or more aryl groups are interrupted by, for example, straight-chain or cyclic alkyl groups or by silyl groups. In addition, 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 heteroaryl ring systems.

[0041] In the context of this invention, cyclic alkyl groups refer to monocyclic, bicyclic, or polycyclic groups.

[0042] In the context of this invention, individual hydrogen atoms or CH2 groups may be replaced by the aforementioned groups, specifically C1 to C2. 20Alkyl groups refer to, 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-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl 1-Methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1-yl, 1,1-dimethyl-n-hept-1-yl, 1,1-dimethyl- 1,1-octyl-1-yl, 1,1-dimethyl-n-decane-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-octyl-1-yl, 1,1-diethyl-n-decane -1-yl, 1,1-diethyl-n-dodecane-1-yl, 1,1-diethyl-n-tetradecane-1-yl, 1,1-diethyl-n-hexadecane-1-yl, 1,1-diethyl-n-octadecane-1-yl, 1-(n-propyl)cyclohexyl-1-yl, 1-(n-butyl)cyclohexyl-1-yl, 1-(n-hexyl)cyclohexyl-1-yl, 1-(n-octyl)cyclohexyl-1-yl and 1-(n-decyl)cyclohexyl-1-yl groups. Alkenyl groups refer to, for example, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl. Alkynyl groups refer to, for example, ethynyl, propynyl, butynyl, penynyl, hexynyl, heptenyl or octynyl. For OR 1 OR 2 The existing C1 to C 20 Alkoxy groups refer to, for example, methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, or 2-methylbutoxy.

[0043] Aromatic or heteroaromatic ring systems having 5-40 aromatic ring atoms, which in each case can be substituted by the aforementioned groups and can be linked to aromatic or heteroaromatic systems via any desired position, refer to groups derived, for example, from substances such as: benzene, naphthalene, anthracene, benzo[a]anthracene, phenanthrene, benzo[a]phenanthrene, pyrene, etc. Perylene, fluoranthene, benzo[a]fluoranthene, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, diphenylenex, terphenyl, ditriphenylenex, fluorene, spirodifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans indo[a]fluorene, cis or trans monobenzo[a]fluorene, cis or trans dibenzo[a]fluorene, trimer indene, isotrimer indene, spirotrimer indene, spiroisotrimer indene, furan Benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indole-carbazole, indole-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-triazole, 1,2,4-triazole, benzo[a]triazole, 1,2,3- diazole, 1,2,4- diazole, 1,2,5- diazole, 1,3,4- Diazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazolium, 1,2,4,5-tetraazine, 1,2,3,4-tetraazine, 1,2,3,5-tetraazine, purine, pteridine, indazine, and benzothiadiazole.

[0044] To further illustrate the compound, a simple structure of formula (1) is shown and elucidated in its entirety below:

[0045]

[0046] In this structure, the subligands coordinated to the two metals M (iridium in this case) are 2-phenylpyrimidine groups. A group of formula (2) is bonded to each of the phenyl and pyrimidine groups, i.e., V in this structure is a group of formula (2). The central ring is a phenyl group in each case, and each of the three A groups is –HC=CH-, i.e., a cis-alkenyl group. The group of formula (2) is also bonded to two subligands L in each case, each of which is a phenylpyridine in the above structure. Therefore, each of the two metals M is coordinated to two phenylpyridine ligands and one phenylpyrimidine ligand in each case in the above structure, wherein the phenyl and pyrimidine groups of the phenylpyrimidine are each coordinated to the two metals M. The subligands here are each linked by a group of formula (2) to form a multi-legged system.

[0047] In the context of this application, the expression “bident subligand” for L means that the unit would be a bidentate ligand if the group of formula (2) or (3) were not present. However, since the hydrogen atom and the connection inside the bridging group of formula (2) or (3) are formally removed in this bidentate ligand, it is not a single ligand but part of the resulting dodecentate ligand (i.e., a ligand with a total of 12 coordination sites), hence the term “subligand” is used for it.

[0048] The bond between the ligand and the metal M can be a coordinate bond or a covalent bond, or the covalent portion of the bond can vary depending on the ligand. When reference is made in this application to the coordination or binding of a ligand or subligand with M, it means, in the context of this application, any kind of bond between the ligand or subligand and M, regardless of the covalent portion of the bond.

[0049] The compounds of the present invention are preferably uncharged, meaning they are electrically neutral. This is achieved by Rh or Ir being in the +III oxidation state in each case. In this case, each of the metals is coordinated by two monoanionic bidentate subligands and one bidentate tetradentate subligand bound to both metals, thus the subligands compensate for the charge of the complexed metal atoms.

[0050] As described above, the two metals M in the compounds of the present invention can be the same or different, and are preferably in the +III oxidation state. Therefore, feasible combinations are Ir / Ir, ​​Ir / Rh, and Rh / Rh. In a preferred embodiment of the present invention, both metals M are Ir(III).

[0051] In a preferred embodiment of the present invention, the compound of formula (1) is selected from compounds of formula (1'):

[0052]

[0053] The R groups at the adjacent positions of D shown herein may be the same or different in each case and are selected from H, D, F, CH3 and CD3, with H being preferred, and the other symbols used have the definitions detailed above.

[0054] As described above, each metal is coordinated in each case by one carbon atom and one nitrogen atom of the central subligand and also by two subligands L. Therefore, the compound of formula (1) has a structure of one of formulas (1a) or (1b), and preferably has a structure of one of formulas (1a') or (1b'):

[0055]

[0056] The R groups explicitly shown therein may be the same or different in each case and are selected from H, D, F, CH3 and CD3, and the other symbols used have the definitions given above. More preferably, the R groups explicitly shown in formulas (1a') and (1b') are H. Structures (1b) and (1b') are particularly preferred.

[0057] The following describes a preferred embodiment of V, namely the group of formula (2) or (3).

[0058] When A in equation (3) 2 When it is CR, especially when all A 2 When both are CR, what's very special is that, in addition, when A 1 A has 0, 1, 2, or 3 groups, especially when 3 are CR2, i.e., when it is a cyclohexyl group. 2 The R groups on the metal can be positioned differently depending on the configuration. Small R groups, such as H or D, are preferred. Preferably, they are all oriented away from the metal (apex) or all oriented towards the metal (intercalation). This will be illustrated below with an example where each A group is an o-phenylene group.

[0059]

[0060] For clarity, the third subligand coordinated to the two metal M are not shown, but are indicated only by dashed bonds. Therefore, it is preferable to present complexes with at least one of two configurations. These are complexes in which all three subligands are arranged equatorially on the central ring.

[0061] Suitable embodiments of the group in formula (2) are those of formulas (5) to (8), and suitable embodiments of the group in formula (3) are those of formulas (9) to (13):

[0062]

[0063]

[0064] The symbols have the definitions given above.

[0065] The preferred R groups in formulas (5) to (13) are as follows:

[0066] 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 an alkenyl group having 2 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of which may be derived from one or more R groups. 1 Group substitution, or having 5 to 24 aromatic ring atoms and in each case being substituted with one or more R groups. 1 Aromatic or heteroaromatic ring systems with substituted groups;

[0067] R 1 In each case, they are the same or different and are H, D, F, CN, OR 2 A straight-chain alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, each of which may be derived from one or more R groups. 2 Group substitution, or having 5 to 24 aromatic ring atoms and in each case being substituted with one or more R groups. 2 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two or more adjacent R groups... 1 Groups together can form a ring system;

[0068] R 2 In each case, they may be the same or different and are H, D, F or an aliphatic, aromatic or heteroaromatic organic group having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may be replaced by F.

[0069] The R groups particularly preferred in formulas (5) to (13) are as follows:

[0070] R may 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 may be represented by one or more R. 1 Group substitution, or having 6 to 12 aromatic ring atoms and in each case being substituted with one or more R groups. 1 Aromatic or heteroaromatic ring systems with substituted groups;

[0071] R 1 In each case, the same or different alkyl groups are H, D, F, CN, straight-chain alkyl groups having 1 to 4 carbon atoms, or branched or cyclic alkyl groups having 3 to 6 carbon atoms, each of which may be derived from one or more R groups.2 Group substitution, or having 6 to 12 aromatic ring atoms and in each case being substituted with one or more R groups. 2 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two or more adjacent R groups... 1 Groups together can form a ring system;

[0072] R 2 In each case, they may be the same or different and are H, D, F, or aliphatic or aromatic hydrocarbon groups having 1 to 12 carbon atoms.

[0073] In a preferred embodiment of the invention, all X groups in formula (2) 1 The groups are all CR, therefore the central trivalent ring in formula (2) is benzene. More preferably, all X 1 The groups are all CH or CD, especially CH. In another preferred embodiment of the invention, all X 1 The groups are all nitrogen atoms, therefore the central trivalent ring of formula (2) is a triazine. Therefore, the preferred embodiment of formula (2) is the structure of formulas (5) and (6) described above. More preferably, the structure of formula (5) is the structure of formula (5'):

[0074]

[0075] The symbols have the definitions given above.

[0076] In another preferred embodiment of the invention, all A groups in formula (3) 2 All groups are CR. More preferably, all A groups are CR. 2 All groups are CH. Therefore, the preferred embodiment of formula (3) is the structure of formula (9) above. More preferably, the structure of formula (9) is one of the following formulas (9') or (9”):

[0077]

[0078] The symbols have the definitions given above, and R is preferably H.

[0079] The preferred A group present in the structures of formulas (2) and (3) and (5) to (13) is described below. The A group may be the same or different in each case and may be an alkenyl group, an amide group, an ester group, an alkylene group, a methyl ether group, or an ortho-bonded arylene or heteroarylene group of formula (4). When A is an alkenyl group, it is a cis-bonded alkenyl group. In the case of an asymmetric A group, any orientation of the group is feasible. This is illustrated schematically below with A = -C(=O)-O- as an example. This results in the following feasible orientations of A, all of which are covered by this invention:

[0080]

[0081] In a preferred embodiment of the invention, A may be the same or different in each case, preferably the same, and is selected from -C(=O)-O-, –C(=O)-NR'-, and groups of formula (4). Furthermore, 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 formula (2) or (3) and the three A groups in the preferred embodiment is:

[0082] A A A Equation (4) Equation (4) Equation (4) –C(=O)-O– –C(=O)-O– –C(=O)-O– –C(=O)-O– –C(=O)-O– Equation (4) –C(=O)-O– Equation (4) Equation (4) –C(=O)-NR'– –C(=O)-NR'– –C(=O)-NR'– –C(=O)-NR'– –C(=O)-NR'– Equation (4) –C(=O)-NR'– Equation (4) Equation (4)

[0083] 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 group having 6 to 24 aromatic ring atoms and in each case may be one or more R's. 1 Aromatic or heteroaromatic ring systems with substituted groups. More preferably, R' may be 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 having 6 to 12 aromatic ring atoms and in each case may be one or more R' groups. 1 The groups are substituted, but preferably unsubstituted, aromatic or heteroaromatic ring systems.

[0084] Preferred embodiments of the group of formula (4) are described below. The group of formula (4) 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 (4) 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 substituents bonded to the group cannot contain heteroatoms. In addition, this definition does not mean that the ring formed by the substituent will not produce a fused aromatic or heteroaromatic structure, such as naphthalene, benzimidazole, etc.

[0085] When the two X in equation (4) 3 When all groups are carbon atoms, the preferred embodiment of the group in formula (4) is the structure of formulas (14) to (30), and when one X in the same ring 3 The group is a carbon atom and another X 3 When the group is a nitrogen atom, the preferred embodiment of the group in formula (4) is the structure of formulas (31) to (38):

[0086]

[0087] The symbols have the definitions given above.

[0088] The six-membered aromatic rings and heteroaromatic rings of formulas (14) to (18) above are particularly preferred. The o-phenylene group, i.e. the group of formula (14) above, is very particularly preferred.

[0089] Simultaneously, adjacent R substituents can also form a cyclic system together, enabling the formation of fused structures, including fused aryl and heteroaryl groups, such as naphthalene, quinoline, benzimidazole, carbazole, dibenzofuran, or dibenzothiophene. Such cyclization is schematically illustrated below with groups of the above formula (14), which can, for example, produce groups of the following formulas (14a) to (14j):

[0090]

[0091] The symbols have the definitions given above.

[0092] Generally, fused groups can be fused to any position in the unit of formula (4), as shown by the fused benzo groups in formulas (14a) to (14c). Groups fused to the unit of formula (4) as in formulas (14d) to (14j) can therefore also be fused to other positions in the unit of formula (4).

[0093] The groups in formula (2) can more preferably be represented by formulas (2a) to (2m), and the groups in formula (3) can more preferably be represented by formulas (3a) to (3m):

[0094]

[0095]

[0096]

[0097] The symbols have the definitions given above. Preferably, X 2 It is the same or different in each case and is CR.

[0098] In a preferred embodiment of the invention, the groups of formula (2a) to (2m) are selected from the groups of formula (5a') to (5m'), and the groups of formula (3a) to (3m) are selected from the groups of formula (9a') to (9m'):

[0099]

[0100]

[0101]

[0102] The symbols have the definitions given above. Preferably, X 2 It is the same or different in each case and is CR.

[0103] A particularly preferred embodiment of the group of formula (2) is the group of formula (5a”):

[0104]

[0105] The symbols have the definitions given above.

[0106] More preferably, the R groups in the above formulas may be the same or different and are H, D, or alkyl groups having 1 to 4 carbon atoms. Most preferably, R = H. Therefore, the structure of the following formula (5a”') is particularly preferred:

[0107]

[0108] The symbols have the definitions given above.

[0109] More preferably, the R groups in the above formulas may be the same or different and are H, D, or alkyl groups having 1 to 4 carbon atoms. Most preferably, R = H. Therefore, the structure of the following formula (5a”') is particularly preferred:

[0110]

[0111] The symbols have the definitions given above.

[0112] The bidentate monoanion subligand L is described below. The subligands L may be the same or different. Preferably, the two subligands L coordinated to the same metal M are identical and have the same substitutions. This preference is due to the simpler synthesis of the corresponding ligands.

[0113] In another preferred embodiment, all four bidentate subligands L are identical and also have the same substitutions.

[0114] In another preferred embodiment of the invention, the coordinating atoms of the bidentate subligands L may be the same or different in each case, and are selected from C, N, P, O, S and / or B, more preferably C, N and / or O, and most preferably C and / or N. These bidentate subligands L 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 subligand L may be the same, or they may be different. Preferably, at least one of the two bidentate subligands L coordinated to the same metal M has one carbon atom and one nitrogen atom, or two carbon atoms as coordinating atoms, especially one carbon atom and one nitrogen atom. More preferably, at least all bidentate subligands have one carbon atom and one nitrogen atom, or two carbon atoms as coordinating atoms, especially one carbon atom and one nitrogen atom. Therefore, metal complexes in which all subligands are ortho-metallized, i.e., forming a metal ring with the metal M, wherein at least one metal-carbon bond is present.

[0115] Furthermore, it is preferred that the metal ring formed by the metal M and the bidentate subligand L is a five-membered ring, particularly when the coordinating atoms are C and N, N and N, or N and O. A six-membered metal ring is also preferred when the coordinating atom is O. This is illustrated schematically below:

[0116]

[0117] 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 an atom of the bidentate subligand L.

[0118] In a preferred embodiment of the invention, each metal M has at least one bidentate subligand L, and more preferably all 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):

[0119]

[0120] The dashed bond represents the bond connecting the subligand L to a group of formula (2) or (3) or, in a preferred embodiment, the group, and the other symbols used are as follows:

[0121] CyC may be the same or different in each case and is a substituted or unsubstituted aryl or heteroaryl group having 5 to 14 aromatic ring atoms and coordinated with M via carbon atoms and covalently bonded to CyD;

[0122] CyD may be the same or different in each case and may be a substituted or unsubstituted heteroaryl group having 5 to 14 aromatic ring atoms and coordinated with M via a nitrogen atom or via a carbene carbon atom and covalently bonded to CyC;

[0123] Meanwhile, two or more optional substituents together can form a cyclic system; in addition, the optional groups are preferably selected from the above-mentioned R groups.

[0124] 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. Furthermore, 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. Furthermore, preferably, the CyC in the subligands of formulas (L-1) and (L-2) is coordinated via an anionic carbon atom.

[0125] When two or more 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. Alternatively, substituents on CyC and CyD in formulas (L-1) and (L-2), or substituents on the two CyD groups in formula (L-3), can also form a ring together, such that CyC and CyD, or the two CyD groups, can also form a single fused aryl or heteroaryl group as a bidentate ligand.

[0126] 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, especially a phenyl group, which is coordinated with a metal via a carbon atom, can be substituted by one or more R groups, and is covalently bonded to CyD.

[0127] Preferred embodiments of the CyC group are structures of the following formulas (CyC-1) to (CyC-20):

[0128]

[0129]

[0130] Whereby CyC binds to CyD at the position indicated by # in each case, and coordinates with the metal at the position indicated by *, R has the definition given above, and the other symbols used are as follows:

[0131] X is the same or different in each case and is CR or N, provided that no more than two symbols X are N in each ring;

[0132] W is NR, O, or S;

[0133] The condition is that when the subligand L is bonded via a CyC group in formula (2) or (3), a symbol X is C and the bridging group of formula (2) or (3) or the preferred embodiment is bonded to that carbon atom. When the subligand L is bonded to a group of formula (2) or (3) via a CyC group, the bonding preferably occurs via the position marked with "o" in the above formula, so in this case the symbol X marked with "o" is preferably C. The above structure without any symbol X marked with "o" is preferably not bonded to a group of formula (2) or (3) because such a bond with the bridging group is disadvantageous for steric reasons.

[0134] Preferably, no more than two symbols X in CyC are N, more preferably no more than one symbol X in CyC is N, and most preferably all symbols X are CR, provided that when CyC is directly bonded to a group of formula (2) or (3), one symbol X is C, and the bridging group of formula (2) or (3) or the preferred embodiment is bonded to the carbon atom.

[0135] Particularly preferred CyC groups are those of the following formulas (CyC-1a) to (CyC-20a):

[0136]

[0137]

[0138] The symbols have the definitions given above, and when CyC is directly bonded to a group of formula (2) or (3), there is no R group, and the group of formula (2) or (3) or the preferred embodiment is bonded to the corresponding carbon atom. When the CyC group is directly bonded to a group of formula (2) or (3), the bonding is preferably carried out via the position marked with "o" in the above formula, so the R group at that position is preferably not present in this case. The above structure that does not contain any carbon atom marked with "o" is preferably not directly bonded to a group of formula (2) or (3).

[0139] Preferred groups among (CyC-1) to (CyC-20) groups are (CyC-1), (CyC-3), (CyC-8), (CyC-10), (CyC-12), (CyC-13) and (CyC-16) groups, and particularly preferred are (CyC-1a), (CyC-3a), (CyC-8a), (CyC-10a), (CyC-12a), (CyC-13a) and (CyC-16a) groups.

[0140] 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, said group being coordinated with a metal via an uncharged nitrogen atom or via a carbene carbon atom and being substituted by one or more R groups and being covalently bonded to CyC.

[0141] Preferred embodiments of the CyD group are structures of the following formulas (CyD-1) to (CyD-14):

[0142]

[0143] The CyD group therein binds to CyC at the position indicated by # and coordinates with a metal at the position indicated by *, and X, W, and R have the definitions given above, provided that when CyD is directly bonded to a group of formula (2) or (3), one symbol X is C, and the bridging group of formula (2) or (3) or the preferred embodiment is bonded to that carbon atom. When the CyD group is directly bonded to a group of formula (2) or (3), the bonding is preferably via the position marked by “o” in the above formula, so the symbol X marked by “o” is preferably C in this case. The above structure without any symbol X marked by “o” is preferably not directly bonded to a group of formula (2) or (3) because such a bond with the bridging group is disadvantageous for steric reasons.

[0144] In this case, the (CyD-1) to (CyD-4), (CyD-7) to (CyD-10), (CyD-13) and (CyD-14) groups are coordinated with the metal via an uncharged nitrogen atom, the (CyD-5) and (CyD-6) groups are coordinated with the metal via a carbene carbon atom, and the (CyD-11) and (CyD-12) groups are coordinated with the metal via an anionic nitrogen atom.

[0145] Preferably, no more than two symbols X in CyD are N, more preferably no more than one symbol X in CyD is N, and particularly preferably all symbols X are CR, provided that when CyD is directly bonded to a group of formula (2) or (3), one symbol X is C, and the bridging group of formula (2) or (3) or preferred embodiment is bonded to the carbon atom.

[0146] Particularly preferred CyD groups are those of the following formulas (CyD-1a) to (CyD-14b):

[0147]

[0148]

[0149] The symbols used have the definitions given above, and when CyD is directly bonded to a group of formula (2) or (3), there is no R group, and the bridging group of formula (2) or (3) or the preferred embodiment is bonded to the corresponding carbon atom. When CyD is directly bonded to a group of formula (2) or (3), the bonding is preferably carried out via the position marked with "o" in the above formula, so the R group at that position is preferably not present in this case. The above structure without any carbon atom marked with "o" is preferably not directly bonded to a group of formula (2) or (3).

[0150] Preferred groups among (CyD-1) to (CyD-14) groups are (CyD-1), (CyD-2), (CyD-3), (CyD-4), (CyD-5) and (CyD-6) groups, especially (CyD-1), (CyD-2) and (CyD-3), and particularly preferred are (CyD-1a), (CyD-2a), (CyD-3a), (CyD-4a), (CyD-5a) and (CyD-6a) groups, especially (CyD-1a), (CyD-2a) and (CyD-3a).

[0151] 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, especially 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.

[0152] In the subligands of formulas (L-1) and (L-2), the preferred (CyC-1) to (CyC-20) and (CyD-1) to (CyD-14) groups described above may be combined with each other as needed, provided that at least one of the CyC or CyD groups has a suitable linking site with a group of formula (2) or (3), the suitable linking site being indicated by "o" in the formula given above. Particularly preferred are the CyC and CyD groups specified above as particularly preferred, namely the groups of formulas (CyC-1a) to (CyC-20a) and the groups of formulas (CyD1-a) to (CyD-14b), combined with each other, provided that at least one of the preferred CyC or CyD groups has a suitable linking site with a group of formula (2) or (3), the suitable linking site being indicated by "o" in the formula given above. Neither CyC nor CyD has such a suitable combination of connection sites with the bridging bases of equation (2) or (3), and therefore is not preferred.

[0153] Very particularly preferred are combinations of one of the (CyC-1), (CyC-3), (CyC-8), (CyC-10), (CyC-12), (CyC-13) and (CyC-16) groups, and especially one of the (CyC-1a), (CyC-3a), (CyC-8a), (CyC-10a), (CyC-12a), (CyC-13a) and (CyC-16a) groups with one of the (CyD-1), (CyD-2) and (CyD-3) groups, and especially with one of the (CyD-1a), (CyD-2a) and (CyD-3a) groups.

[0154] 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):

[0155]

[0156] The symbols used have the definitions given above, * indicates the coordination position with iridium, and “o” represents the bonding position with the group of formula (2) or (3).

[0157] 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):

[0158]

[0159] The symbols used have the definitions given above, and “o” represents the bonding position with the group in formula (2) or (3).

[0160] The preferred CyD groups in the subligands of formula (L-3) can also be combined with each other as needed by combining uncharged CyD groups, i.e., (CyD-1) to (CyD-10), (CyD-13) or (CyD-14) groups, with anionic CyD groups, i.e. (CyD-11) or (CyD-12) groups, provided that at least one of the preferred CyD groups has a suitable linking site with a group of formula (2) or (3), and the suitable linking site is indicated by "o" in the formula given above.

[0161] When two R groups, wherein in formulas (L-1) and (L-2) one is bonded to CyC and the other to CyD, or in formula (L-3) one is bonded to one CyD group and the other to another CyD group, form an aromatic ring system with each other, this can result in bridging subligands as well as subligands that collectively represent a single, larger heteroaryl group, such as benzo[h]quinoline, etc. Cycloning between substituents on CyC and CyD in formulas (L-1) and (L-2) or between substituents on the two CyD groups in formula (L-3) is preferably via a group according to one of the following formulas (39) to (48):

[0162]

[0163] Where R 1 With the definitions given above, and the dashed bond indicates a bond connected to CyC or CyD. Meanwhile, the asymmetric groups mentioned above can be incorporated into each of the two possible orientations; for example, in the group of formula (48), the oxygen atom can be bonded to the CyC group and the carbonyl group to the CyD group, or the oxygen atom can be bonded to the CyD group and the carbonyl group to the CyC group.

[0164] At the same time, when this leads to cyclization to obtain a six-membered ring as shown in formulas (L-22) and (L-23) for example, the group of formula (45) is particularly preferred.

[0165] Preferred ligands produced by cyclization between two R groups in different rings are those of formulas (L-4) to (L-31) shown below:

[0166]

[0167]

[0168] The symbols used have the definitions given above, and “o” indicates the binding position of the subligand with the group of formula (2) or (3).

[0169] In a preferred embodiment of the subligands of formulas (L-4) to (L-31), a total of one symbol X is N, and the other symbols X are CR, or all symbols X are CR.

[0170] In another embodiment of the invention, preferably, in groups (CyC-1) to (CyC-20) or (CyD-1) to (CyD-14), or in the subligands (L-1-1) to (L-2-3), (L-4) to (L-31), when the R group bonded as a substituent adjacent to the nitrogen atom is not hydrogen or deuterium, one of the atoms X is N. This similarly applies to preferred structures (CyC-1a) to (CyC-20a) or (CyD-1a) to (CyD-14b), wherein the substituent bonded adjacent to the non-coordinated nitrogen atom is preferably an R group that is not hydrogen or deuterium. In this case, the substituent R is preferably selected from groups such as CF3, OR 1 (where R) 1 It is an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, particularly a branched or cyclic alkyl group having 3 to 10 carbon atoms, a dialkylamino group having 2 to 10 carbon atoms, an aromatic or heteroaromatic cyclic system, or an aralkyl or heteroaromatic alkyl group. These groups are spatially demanding groups. Furthermore, preferably, the R group may also form a ring with an adjacent R group.

[0171] Another suitable bidentate subligand is a subligand of the following formula (L-32) or (L-33).

[0172]

[0173] Where R has the definition given above, * represents the coordination position with the metal, "o" represents the connection position of the subligand with the group of formula (2) or (3), and the other symbols used are as follows:

[0174] X is the same or different in each case and is CR or N, provided that no more than one symbol X in each ring is N, and further provided that one symbol X is C and the subligand is bonded to the group of formula (2) or (3) via the carbon atom.

[0175] 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 (49):

[0176]

[0177] The dashed bond represents the bond of the group within the ligand, and Y is the same or different in each case and is CR. 1Or N, and preferably no more than one symbol Y is N. In a preferred embodiment of the subligands (L-32) or (L-33), there is no more than one group of formula (50). In a preferred embodiment of the invention, in the subligands of formulas (L-32) and (L-33), a total of 0, 1, or 2 of the symbols X and possible Ys are N. More preferably, a total of 0 or 1 of the symbols X and possible Ys are N.

[0178] Other suitable bidentate subligands are structures of formulas (L-34) to (L-38), wherein preferably no more than one of the two bidentate subligands L for each metal is one of these structures.

[0179]

[0180] The subligands (L-34) to (L-36) are each coordinated to the metal via a nitrogen atom and a negatively charged oxygen atom as explicitly shown, and the subligands (L-37) and (L-38) are coordinated to the metal via two oxygen atoms, X has the definition given above, and “o” indicates the binding position of the subligand L with the group of formula (2) or (3).

[0181] For the subligands of formulas (L-34) to (L-36), the above-described preferred embodiments of X are also preferred.

[0182] The preferred subligands of formulas (L-34) to (L-36) are therefore the subligands of formulas (L-34a) to (L-36a):

[0183]

[0184] The symbols used have the definitions given above, and “o” indicates the binding position of the subligand L with the group of formula (2) or (3).

[0185] More preferably, in these formulas, R is hydrogen, where “o” indicates the position of the subligand L within the group of formula (2) or (3) or the preferred embodiment, and thus the structures are those of formulas (L-34b) to (L-36b):

[0186]

[0187] The symbols used have the definitions given above.

[0188] The following describes preferred substituents that can exist on the aforementioned subligands and also on A when A is a group of formula (4).

[0189] In a preferred embodiment of the invention, the compound of the invention contains two substituents R, which 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 (2) or (3) or in the preferred embodiment and / or on one or more bidentate subligands L. The aliphatic ring formed by cyclization of the two substituents R together is preferably described by one of the following formulas (50) to (56):

[0190]

[0191]

[0192] Where R 1 and R 2 As defined above, a dashed bond represents the connection between two carbon atoms in a ligand, and additionally:

[0193] Z 1 Z 3 The same or different in each case and is C(R) 3 )2, O, S, NR 3 Or C (=O);

[0194] Z 2 It is C(R) 1 )2, O, S, NR 3 Or C (=O);

[0195] G is a carbon atom with 1, 2, or 3 carbon atoms and can be generated by one or more R atoms. 2 Substituted alkyl subunits, -CR 2 =CR 2 -or has 5 to 14 aromatic ring atoms and can be converted by one or more R 2 A group-substituted ortho-bonded arylene or heteroarylene group;

[0196] R 3 In each case, the same or different and being 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 Instead, or having 5 to 24 aromatic ring atoms and in each case being one or more R2 Aromatic or heteroaromatic ring systems with substituted groups, or having 5 to 24 aromatic ring atoms and being substituted by one or more R groups. 2 A group-substituted aryloxy or heteroaryloxy group; simultaneously, two R groups bonded to the same carbon atom. 3 The groups together can form aliphatic or aromatic ring systems and thus spirocyclic systems; additionally, R 3 With adjacent R or R 1 The group can form an aliphatic ring system;

[0197] The condition 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.

[0198] In a preferred embodiment of the present invention, R 3 Not H.

[0199] In the structures described above in formulas (50) to (56) and in other embodiments of these structures designated as preferred, a double bond is formally drawn between the two carbon atoms. This is a simplification of the following chemical structures, wherein the two carbon atoms are incorporated into an aromatic or heteroaromatic system and therefore the bond between the two carbon atoms is formally intermediate between the bond order of a single bond and the bond order of a double bond. Therefore, the drawing of the formal double bond should not be interpreted as a limitation on the structure; rather, it will be apparent to those skilled in the art that this is an aromatic bond.

[0200] When adjacent groups in the structure of this invention form an aliphatic ring system, it is preferable that the latter does not have any acidic benzylic protons. A benzylic proton is a proton bonded to a carbon atom directly bonded to a ligand. This can be achieved by completely replacing the carbon atom in the aliphatic ring system that is directly bonded to an aryl or heteroaryl group and by removing any bonded hydrogen atoms. Therefore, the absence of acidic benzylic protons in formulas (50) to (52) is achieved by Z 1 and Z 3 When they are C(R) 3 When )2 is defined as such that R 3 It is not achieved by hydrogen. Alternatively, this can also be achieved by the carbon atom in the aliphatic ring system that is directly bonded to the aryl or heteroaryl group being a bridgehead in a bicyclic or polycyclic structure. Due to the spatial structure of bicyclic or polycyclic rings, the acidity of the proton bonded to the bridgehead carbon atom is significantly lower than that of the benzyl proton, which is not bonded to the carbon atom in the bicyclic or polycyclic structure and is considered a non-acidic proton in the context of this invention. Therefore, the absence of acidic benzyl protons in formulas (53) to (56) is achieved through their bicyclic structure; therefore, when R... 1 When it is H, R 1 The acidity is much lower than that of the benzylic proton because the corresponding anion of the bicyclic structure is not median-stable. Even when R in equations (53) to (56) 1When it is H, it is therefore a non-acid proton in the context of this application.

[0201] In a preferred embodiment of the structure of equations (50) to (56), Z 1 Z 2 and Z 3 No more than one of the functional 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 The same or different in each case and whether it 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 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 CH2.

[0202] Preferred embodiments of formula (50) are therefore the structures of formulas (50-A), (50-B), (50-C), and (50-D), and a particularly preferred embodiment of formula (50-A) is the structure of formulas (50-E) and (50-F):

[0203]

[0204] Where R 1 and R 3 Given the definition above, and Z 1 Z 2 and Z 3 The same or different in each case and whether it is O or NR 3 .

[0205] The preferred embodiment of formula (51) is the structure of formulas (51-A) to (51-F):

[0206]

[0207] Where R 1 and R 3 Given the definition above, and Z 1 Z 2 and Z 3 The same or different in each case and whether it is O or NR 3 .

[0208] The preferred embodiment of formula (52) is the structure of formulas (52-A) to (52-E):

[0209]

[0210] Where R 1 and R 3 Given the definition above, and Z 1 Z 2 and Z 3 The same or different in each case and whether it is O or NR 3 .

[0211] In a preferred embodiment of the structure of equation (53), R is bonded to the bridge head. 1 The functional group is H, D, F, or CH3. Preferably, Z is also present. 2 It is C(R) 1 )2 or O, and more preferably C(R) 3 2. The preferred embodiment of formula (53) is therefore the structure of formulas (53-A) and (53-B), and a particularly preferred embodiment of (53-A) is the structure of formula (53-C):

[0212]

[0213] The symbols used have the definitions given above.

[0214] In a preferred embodiment of the structures of equations (54), (55), and (56), R is bonded to the bridge abutment. 1 The functional group is H, D, F, or CH3. Preferably, Z is also present. 2 It is C(R) 1 2. Preferred embodiments of equations (54), (55), and (56) are therefore the structures of equations (54-A), (55-A), and (56-A):

[0215]

[0216] The symbols used have the definitions given above.

[0217] Furthermore, preferably, the G group in formulas (53), (53-A), (53-B), (53-C), (54), (54-A), (55), (55-A), (56), and (56-A) is a 1,2-ethenyl group, and the group can be generated by one or more R groups. 2 Group substitution, wherein R 2 Preferably, in each case, the same or different groups are H or alkyl groups having 1 to 4 carbon atoms, or have 6 to 10 carbon atoms and can be composed of one or more R groups.2 Substituted but preferably unsubstituted o-arylene groups, particularly those that can be substituted by one or more R groups. 2 The group is substituted, but preferably unsubstituted, with an o-phenylene group.

[0218] In another preferred embodiment of the invention, in the groups of formulas (50) to (56) and in the preferred embodiment R 3 In each case, the same or different and being 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 hydrogen atom can be replaced by D or F, or it has 5 to 14 aromatic ring atoms and in each case can be replaced by one or more R atoms. 2 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two R groups bonded to the same carbon atom. 3 Groups can combine to form aliphatic or aromatic ring systems and thus spirocyclic systems; additionally, R 3 Can be with adjacent R or R 1 The groups form aliphatic ring systems.

[0219] In a particularly preferred embodiment of the invention, in the groups of formulas (50) to (56) and in the preferred embodiment R 3 In each case, the same or different and being F, a straight-chain alkyl group having 1 to 3 carbon atoms, especially methyl, or having 5 to 12 aromatic ring atoms and in each case being one or more R 2 The aromatic or heteroaromatic ring system is substituted, but preferably unsubstituted; simultaneously, the two R groups bonded to the same carbon atom... 3 Groups can together form aliphatic or aromatic ring systems and thus spirocyclic systems; additionally, R 3 Can be with adjacent R or R 1 The groups form aliphatic ring systems.

[0220] Particularly suitable examples of groups of formula (50) are the following groups:

[0221]

[0222]

[0223] Examples of particularly suitable groups of formula (51) are the following groups:

[0224]

[0225] Examples of particularly suitable groups of formulas (52), (55) and (56) are the following groups:

[0226]

[0227] Examples of particularly suitable groups of formula (53) are the following groups:

[0228]

[0229] Examples of particularly suitable groups of formula (54) are the following groups:

[0230]

[0231] When the R group is bonded to a bidentate subligand or ligand, or to a divalent aromatic or heteroaromatic group of formula (4) bonded in formula (2) or (3) or, in preferred embodiments, these R groups may be 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, or an alkenyl group having 2 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl or alkenyl group in each case may be one or more R 1 Group substitution, or having 5 to 30 aromatic ring atoms and in each case being substituted with one or more R groups. 1 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two adjacent R groups together or R with R 1 Together, they can form monocyclic or polycyclic aliphatic or aromatic ring systems. More preferably, these R groups may be 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 having 5 to 24 aromatic ring atoms and in each case may be replaced by one or more R atoms. 1 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two adjacent R groups together or R with R 1 Together they can form monocyclic or polycyclic aliphatic or aromatic ring systems.

[0232] Preferred bond to R of R 1 The functional groups may be 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, or an alkenyl group having 2 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein the alkyl group in each case may be one or more R 2 Group substitution, or having 5 to 24 aromatic ring atoms and in each case being substituted with one or more R groups. 2 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two or more adjacent R groups... 1 The groups together can form monocyclic or polycyclic aliphatic ring systems. Particularly preferred are R groups bonded to R. 1 The groups may be 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 may be derived from one or more R groups. 2 Group substitution, or having 5 to 13 aromatic ring atoms and in each case being substituted with one or more R groups. 2 Aromatic or heteroaromatic ring systems with substituted groups; simultaneously, two or more adjacent R groups... 1 The groups together can form monocyclic or polycyclic aliphatic ring systems.

[0233] Preferred R 2 The groups may be the same or different in each case and are H, F, or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms; meanwhile, two or more R 2 Substituents can also form monocyclic or polycyclic aliphatic ring systems.

[0234] The preferred embodiments described above can be combined with each other as needed. In a particularly preferred embodiment of the present invention, all the preferred embodiments described above are applicable simultaneously.

[0235] The compounds of this invention are chiral. Depending on the exact structure of the complex and ligands, diastereomers and several pairs of enantiomers can be formed. In this case, the complexes of this invention comprise different diastereomers or corresponding racemates and individual separate diastereomers or mixtures of enantiomers.

[0236] Suitable examples of the compounds of the present invention are the structures shown in the table below.

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246] In ortho-metallization reactions of ligands, the corresponding bimetallic complexes are typically obtained as ΛΛ and ΔΔ isomers, as well as mixtures of ΔΛ and ΛΔ isomers. The ΛΛ and ΔΔ isomers form an enantiomer pair, and so do the ΔΛ and ΛΔ isomers. Diastereomer pairs can be separated by conventional methods, such as chromatography or fractional crystallization. Depending on the symmetry of the ligands, the stereocenters can coincide, thus meso forms are also possible. For example, C 2v Or C s Ortho-metallization of symmetrical ligands yields ΛΛ and ΔΔ isomers (racemic, C2 symmetric) and ΛΔ isomers (meta-compound, C2 symmetric). s (Symmetrical). The preparation and separation of diastereomer pairs will be illustrated in the following examples.

[0247]

[0248] The separation of racemic products of the ΔΔ and ΛΛ isomers can be achieved via stepwise crystallization of diastereomeric salt pairs or by conventional methods on a chiral column. For this purpose, one option is to oxidize the uncharged Ir(III) complex (e.g., with peroxide or H₂O₂ or by electrochemical means), add an enantiomerically pure monoanionic base (chiral base) salt to the resulting cationic Ir(III) / Ir(IV) complex or dicationically cationic Ir(IV) / 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 enantiomerically pure uncharged complex, as illustrated below:

[0249]

[0250] Enantiomerically pure complexes can also be selectively synthesized as shown in the following scheme. For this purpose, as described above, the diastereomer pairs formed in ortho-metallization are separated, brominated, and then reacted with boric acid R*AB(OH)2 containing a chiral R* group (preferably >99% enantiomeric excess) via a cross-coupling reaction. The resulting diastereomer pairs can be separated using conventional methods by silica gel chromatography or by stepwise crystallization. In this way, enantiomerically enriched or enantiomerically pure complexes are obtained. Subsequently, the chiral group can optionally be eliminated or may be retained in the molecule.

[0251]

[0252]

[0253] Typically, complexes in ortho-metallization are obtained as a mixture of diastereomer pairs. However, depending on the ligand structure, it is also possible to selectively synthesize only one of the diastereomer pairs, since the other is formed only in small amounts (if any) for steric reasons. This will be illustrated by the following examples.

[0254]

[0255] Meso compounds (if any) occur to a very small extent due to the unfavorable interaction between the phenyl group at position 5 on the pyridine ring (with a rectangular boundary) and the phenyl group at the head of one of the other subligands (also with a rectangular boundary). Racemic compounds are formed preferentially or only.

[0256] The complexes of the present invention can be prepared in particular by the methods described below. For this purpose, a 12-dentate ligand is prepared and then coordinated with metal M by an ortho-metallization reaction. Typically, for this purpose, an iridium or rhodium salt is reacted with the corresponding free ligand.

[0257] Therefore, the present invention also provides a method for preparing the compounds of the present invention by reacting the corresponding free ligand with a metal alkoxide of formula (57), a metal ketone of formula (58), a metal halide of formula (59), or a metal carboxylate of formula (60).

[0258]

[0259] Where M and R have the definitions given above, Hal = F, Cl, Br or I, and the iridium reactant or rhodium reactant may also be in the form of the corresponding hydrate. Here, R is preferably an alkyl group having 1 to 4 carbon atoms.

[0260] Iridium or rhodium compounds with alkoxide and / or halide anions and / or hydroxyl groups, as well as ketone anion groups, can also be used. These compounds may also be charged. Relevant iridium compounds particularly suitable as reactants are disclosed in WO 2004 / 085449. [IrCl2(acac)2] is particularly suitable. ─ For example, Na[IrCl2(acac)2], metal complexes with acetylacetonate derivatives as ligands, such as Ir(acac)3 or tris(2,2,6,6-tetramethylheptane-3,5-dione oxy)iridium, and IrCl3·xH2O, where x is usually a number from 2 to 4.

[0261] 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 heating or photochemical methods and / or by microwave radiation. Alternatively, the synthesis can be carried out in an autoclave under high pressure and / or high temperature.

[0262] The reaction can be carried out in the melt of the corresponding ligand to be metallized at the ortho position without the addition of a solvent or melt additive. Optionally, a solvent or melt additive 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, propylene-1,2-diol, 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, heteroaromatic 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 aids 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, triphenylide, R-naphthol or S-naphthol or their corresponding racemic derivatives, 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.

[0263] These methods, followed by purification if necessary, such as recrystallization or sublimation, can yield high purity, preferably greater than 99% (via...). 1 The compound of formula (1) of the present invention is determined by ¹H NMR and / or HPLC.

[0264] The compounds of the present invention can also become soluble through appropriate substitution, for example, by relatively long-chain 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 groups. Another particular method that results in a significant improvement in the solubility of the metal complex is the use of fused aliphatic groups, such as those shown, for example, by formulas (50) to (56) disclosed above. Thus, these compounds dissolve in sufficient concentrations in standard organic solvents (e.g., toluene or xylene) at room temperature to allow the complex to be processed from solution. These soluble compounds are particularly suitable for processing from solution, for example, by printing methods.

[0265] To process the metal complexes of the present invention from the liquid phase, for example 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, mixtures of two or more solvents are preferred. Suitable and preferred solvents include, for example, toluene, anisole, o-xylene, m-xylene or p-xylene, methyl benzoate, mesitylene, naphthalene, o-dimethoxybenzene, THF, methyl-THF, THP, chlorobenzene, dimethylbenzene, etc. Alkane, phenoxytoluene, especially 3-phenoxytoluene, (-)-fonone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decahydronaphthalene, dodecane Benzene, ethyl benzoate, indene, methyl benzoate, NMP, p-methylisopropylbenzene, phenethyl ether, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentabenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, hexamethylindene, or mixtures of these solvents.

[0266] Therefore, 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 also be another organic or inorganic compound also used in electronic devices, such as a matrix material. This additional compound may also be polymerized.

[0267] The metal complexes of the present invention described above, or the preferred embodiments detailed above, can be used in electronic devices as active components or as oxygen sensitizers. Therefore, the present invention also provides the use of the compounds of the present invention in electronic devices or as oxygen sensitizers. The present invention further provides electronic devices comprising at least one compound of the present invention.

[0268] An electronic device is any device comprising an anode, a cathode, and at least one layer containing at least one organic or organometallic compound. Therefore, the electronic device of the present invention comprises 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 (OLED, PLED), organic integrated circuits (O-IC), organic field-effect transistors (O-FET), organic thin-film transistors (O-TFT), organic light-emitting transistors (O-LET), and organic solar cells (O-SC) (organic solar cells refer to pure organic solar cells and dye-sensitized solar cells). Organic electroluminescent devices include organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQDs), light-emitting electrochemical cells (LECs), oxygen sensors, and organic laser diodes (O-lasers), wherein said devices contain at least one metal complex of the present invention in at least one layer. Organic electroluminescent devices are particularly preferred. The active component is typically an organic or inorganic material introduced between the anode and cathode, such as charge-injecting, charge-transporting, or charge-blocking materials, but particularly luminescent and matrix materials. The compounds of the present invention exhibit particularly good properties as luminescent materials in organic electroluminescent devices. Therefore, a preferred embodiment of the present invention is an organic electroluminescent device. In addition, the compounds of the present invention can be used to generate singlet oxygen or for photocatalysis.

[0269] The organic electroluminescent device includes a cathode, an anode, and at least one light-emitting layer. In addition to these layers, it may also include other layers, such as 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 in each case. Simultaneously, one or more hole transport layers may be p-type doped, for example, with metal oxides such as MoO3 or WO3 or with (per)fluorinated electron-deficient aromatic systems, and / or one or more electron transport layers may be n-type doped. Intermediate layers may 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 single one of these layers is necessary.

[0270] In this context, the organic electroluminescent device may include a single emitting layer, or it may include multiple emitting layers. If multiple emitting layers are present, these preferably have a total of multiple emission peaks between 380 nm and 750 nm, resulting in white emission; in other words, multiple luminescent compounds capable of fluorescence or phosphorescence are used in the emitting layers. A three-layer system, wherein the three layers exhibit blue, green, and orange or red emission, or a system with more than three emitting layers is particularly preferred. Furthermore, tandem OLEDs are preferred. The system may also be a hybrid system, wherein one or more layers fluoresce and one or more other layers phosphorescent. White-emitting organic electroluminescent devices can be used in lighting applications or, in conjunction with color filters, in full-color displays.

[0271] 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.

[0272] 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. The mixture of the metal complex and 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, based on the total mixture of the luminescent material and matrix material. Accordingly, 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, based on the total mixture of the luminescent material and matrix material.

[0273] The matrix material used can typically be any material known for this purpose according to existing technology. Preferably, the triplet energy level of the matrix material is higher than that of the luminescent material.

[0274] The matrix materials suitable for the compounds of this invention are ketones, phosphine oxides, sulfoxides and sulfones, such as those according to WO 2004 / 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, US 2005 / 0069729, JP 2004 / 288381, EP 1205527, WO 2008 / 086851 or US 2009 / 0134784, indolecarbazole derivatives, such as those according to WO 2007 / 063754 or WO 2008 / 056746, indobenzocarbazole derivatives, such as those according to WO2010 / 136109 or WO 2011 / 000455, azacarbazole, such as those according to EP 1617710, EP 1617711, EP1731584, JP 2005 / 347160, dipolar matrix materials, such as those according to WO 2007 / 137725, silanes, such as those according to WO 2005 / 111172, azaborone or borate esters, such as those according to WO 2006 / 117052, diazasilone derivatives, such as those according to WO 2010 / 054729, diazaphosphonone derivatives, such as those according to WO2010 / 054730, triazine derivatives, such as those according to WO Zinc complexes, such as those according to 2010 / 015306, WO 2007 / 063754 or WO 2008 / 056746, dibenzofuran derivatives, such as those according to EP 652273 or WO 2009 / 062578, or bridged carbazole derivatives, such as those according to US 2009 / 0136779, WO 2010 / 050778, WO 2011 / 042107 or WO 2011 / 088877.

[0275] Examples of compounds suitable as matrix materials for the compounds of the present invention are described below.

[0276] Examples of triazines and pyrimidines that can be used as electron transport matrix materials are the following compounds:

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289]

[0290] Examples of lactams that can be used as electron transport matrix materials are the following compounds:

[0291]

[0292]

[0293]

[0294]

[0295]

[0296]

[0297] Examples of ketones that can be used as electron transport matrix materials are the following compounds:

[0298]

[0299]

[0300]

[0301]

[0302]

[0303] Examples of metal complexes that can be used as electron transport matrix materials are the following compounds:

[0304]

[0305] Examples of phosphine oxides that can be used as electron transport matrix materials include the following compounds:

[0306]

[0307]

[0308] The most generalized examples of indobenzocarbazole and indobenzocarbazole derivatives that can be used as hole or electron transport matrix materials according to their substitution patterns are the following compounds:

[0309]

[0310]

[0311]

[0312]

[0313] Examples of carbazole derivatives that can be used as hole or electron transport matrix materials according to their substitution patterns are the following compounds:

[0314]

[0315]

[0316] Examples of bridging carbazole derivatives that can be used as hole transport matrix materials are the following compounds:

[0317]

[0318]

[0319]

[0320]

[0321]

[0322] Examples of biscarbazole compounds that can be used as hole transport matrix materials include the following compounds:

[0323]

[0324]

[0325]

[0326]

[0327] Examples of amines that can be used as hole-conducting matrix materials are the following compounds:

[0328]

[0329]

[0330]

[0331] Examples of materials that can be used as wide-bandgap matrix materials are the following compounds:

[0332]

[0333]

[0334] It is also preferable 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 the triplet emitter for longer wavelength emission, such as for a triplet emitter emitting green or red light. In this case, it is also preferable that both the metal complex for shorter and longer wavelength emission are compounds of the present invention. Compounds suitable for this purpose are in particular the compounds disclosed in WO 2016 / 124304 and WO 2017 / 032439.

[0335] Examples of suitable triplet luminescent organisms that can be used as co-dopersants for the compounds of the present invention are described in the table below.

[0336]

[0337]

[0338]

[0339]

[0340]

[0341]

[0342]

[0343]

[0344]

[0345] Furthermore, it is preferable to use a variety of different matrix materials in mixture form, 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 matrix for the metal complexes of the present invention. It is also preferable to use a mixture of a charge-transporting matrix material and an electrically inert matrix material that, even if involved, does not significantly participate in 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.

[0346] Furthermore, it is preferable to use a mixture of two or more triplet emitters and a matrix. The triplet emitter having a shorter wavelength emission spectrum is used herein as a co-matrix for the triplet emitter having a longer wavelength emission spectrum. For example, the metal complexes of the present invention can therefore be used as a co-matrix for longer wavelength emitting triplet emitters, such as for triplet emitters emitting green or red light. It is also preferred that both the shorter and longer wavelength emitting metal complexes are compounds of the present invention. Examples of metal complexes that can be used as a co-matrix are the metal complexes disclosed in WO 2016 / 124304 and WO 2017 / 032439.

[0347] Depending on the exact structure of the ligands, 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.

[0348] The preferred cathode is a metal with low work function, comprising a metal alloy or multilayer structure of various metals 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 containing alkali metals or alkaline earth metals and silver, such as alloys containing magnesium and silver. In the case of a multilayer structure, other metals with relatively high work function, such as Ag, can also be used in addition to the aforementioned metals; in this case, combinations of metals such as Mg / Ag, Ca / Ag, or Ba / Ag are typically used. It is also preferable to introduce a thin interlayer of material with a high dielectric constant between the metal cathode and the organic semiconductor. Examples of materials suitable for this purpose are alkali metal 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 suitable for this purpose. The thickness of this layer is preferably 0.5 to 5 nm.

[0349] 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, such as Ag, Pt, or Au, are suitable for this purpose. Secondly, metal / metal oxide electrodes (e.g., Al / Ni / NiO) are also preferred. x Al / PtO x For some applications, at least one electrode must be transparent or partially transparent to enable organic material radiation (O-SC) or light emission (OLED / PLED, O-laser). Preferred anode materials are conductive mixed metal oxides. Indium tin oxide (ITO) or indium zinc oxide (IZO) are particularly preferred. Furthermore, conductive doped organic materials are preferred, especially conductive doped polymers such as PEDOT, PANI, or derivatives of these polymers. Additionally, it is preferable to apply a p-type doped hole-transporting material to the anode as a hole injection layer; suitable p-type dopants in this case are metal oxides, such as MoO3 or WO3, or (per)fluorinated electron-deficient aromatic systems. Other suitable p-type dopants are HAT-CN (hexacyanohexaazatriphenylide) or NPD9 from Novaled. This layer simplifies hole injection into materials with low HOMO, i.e., numerically high HOMO.

[0350] In the other layers, any material as 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.

[0351] The devices are structured accordingly (depending on the application), with contact connections and ultimately hermetically sealed, because the lifespan of these devices is severely shortened in the presence of water and / or air.

[0352] Another preferred organic electroluminescent device is characterized by coating one or more layers via a sublimation method. In this case, in a vacuum sublimation system, typically less than 10 -5 millibars, preferably less than 10 -6 The material is applied via vapor deposition at an initial pressure of millibars. The initial pressure can also be lower or higher, for example, less than 10. -7 millibar.

[0353] The organic electroluminescent device is also preferably 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 particular example of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is applied directly through a nozzle and thus structured.

[0354] Another preferred organic electroluminescent device is 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) 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.

[0355] The organic electroluminescent device can also be fabricated as a hybrid system by applying one or more layers from a solution and by applying one or more other layers via 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 thereto by vapor deposition under reduced pressure.

[0356] These methods are generally known to those skilled in the art and can be applied by those skilled in the art without difficulty to compounds comprising formula (1) or (2) or organic electroluminescent devices of the preferred embodiments described above.

[0357] The electronic devices of the present invention, particularly organic electroluminescent devices, have one or more of the following surprising advantages over the prior art:

[0358] 1. The compounds of the present invention exhibit very high photoluminescence quantum yields. When used in organic electroluminescent devices, this results in excellent efficiency.

[0359] 2. The compounds of the present invention have a very short luminescence lifetime. When used in organic electroluminescent devices, this results in improved roll-off characteristics and also leads to higher luminescence quantum yield by avoiding nonradiative relaxation channels.

[0360] These advantages are not accompanied by a deterioration in other electronic properties.

[0361] The invention is illustrated in more detail by way of the following examples, but is not intended to limit the invention thereto. Those skilled in the art will be able to use the details given to make other electronic devices of the invention and thus practice the invention throughout the claimed scope without inventive effort. Example:

[0362] Unless otherwise specified, the following synthesis was carried out in an anhydrous solvent under a protective gas atmosphere. Metal complexes were further treated in the dark or under yellow light. Solvents and reagents can be purchased from, for example, Sigma-Aldrich or ABCR. The numbers in square brackets or the reference numbers for individual compounds refer to the CAS numbers of compounds known from the literature.

[0363] A: Synthesis of Synthetic Units

[0364] Example B1:

[0365]

[0366] 31.4 g (100 mmol) of 5,5'-dibromo-2,2'-bipyridine [15862-18-7], 54.6 g (215 mmol) of bis(pinacolyl)diborane [73183-34-3], 58.9 g (600 mmol) of potassium acetate, 2.3 g (8 mmol) of SPhos [657408-07-6], 1.3 mg (6 mmol) of palladium(II) acetate, and 900 ml of 1,4-dibromo-2,2'-bipyridine [15862-18-7] were added. The mixture of alkanes was heated under reflux for 16 hours. Dialkyl was removed on a rotary evaporator. The black residue was treated by extraction with 1000 ml of ethyl acetate and 500 ml of water in a separatory funnel. The organic phase was washed once with 300 ml of water and once with 150 ml of saturated sodium chloride solution, and then filtered through a silica gel bed. The silica gel was washed with 2 × 250 ml of ethyl acetate. The filtrate was dried over sodium sulfate and concentrated. The residue was mixed with 400 ml of n-heptane, and the suspension was heated to reflux for 1 hour. After cooling, the solid was filtered off and washed twice with 30 ml of n-heptane each time. Yield: 33.1 g (81 mmol), 81%. Purity: according to 1 The H NMR is approximately 98%.

[0367] Example B2:

[0368]

[0369] Compound B2 can be prepared using a similar procedure to that of B1, except that 5-bromo-2-(4-bromophenyl)pyrimidine [1263061-48-8] is used instead of 5,5'-dibromo-2,2'-bipyridine.

[0370] Example B3:

[0371]

[0372] A mixture of 40.8 g (100 mmol) of B1, 56.6 g (200 mmol) of 1-bromo-2-iodobenzene [583-55-1], 63.6 g (600 mmol) of sodium carbonate, 5.8 g (5 mmol) of tetrakis(triphenylphosphine)palladium(0) [14221-01-3], 1000 ml of 1,2-dimethoxyethane, and 500 ml of water was heated under reflux for 60 hours. After cooling, the precipitated solid was filtered off and washed three times with 100 ml of ethanol. The crude product was dissolved in 1000 ml of dichloromethane (DCM) and filtered through a silica gel bed as a DCM slurry. The silica gel was washed three times with 100 ml of ethyl acetate each time. The dichloromethane was removed by a rotary evaporator cooled to 500 mbar at a bath temperature of 50 °C. The solid precipitated from the remaining ethyl acetate was filtered off and washed twice with 20 ml of ethyl acetate. The resulting solid was recrystallized again from boiling ethyl acetate. Yield: 25.6g (55mmol), 55%, according to 1 The H NMR value is 95%.

[0373] Example B4:

[0374]

[0375] Compound B4 can be prepared using a similar procedure to B3, except that unit B2 is used instead of B1. Yield: 52%.

[0376] Example B5:

[0377]

[0378] Compound B5 can be prepared using a similar procedure to B3, except that 1-bromo-2-chlorobenzene [694-80-4] is used instead of 1-bromo-2-iodobenzene. Purification was achieved by chromatography on a Torrent automated rapid column system from Axel-Semrau. Yield: 67%.

[0379] Example B6:

[0380]

[0381] Compound B6 can be prepared using a similar procedure to B4, except that 1-bromo-2-chlorobenzene is used instead of 1-bromo-2-iodobenzene. Purification was achieved by chromatography on a Torrent automated rapid column system from Axel-Semrau. Yield: 70%.

[0382] Example B8:

[0383]

[0384] A mixture of 18.1 g (100 mmol) of 6-chlorotetrahydronaphthone [26673-31-4], 16.5 g (300 mmol) of propargylamine [2450-71-7], 796 mg (2 mmol) of sodium tetrachloroaurate(III) dihydrate, and 200 mL of ethanol was stirred in an autoclave at 120 °C for 24 hours. After cooling, the ethanol was removed under reduced pressure, and the residue was dissolved in 200 mL of ethyl acetate. The solution was washed three times with 200 mL of water and once with 100 mL of saturated sodium chloride solution, dried over magnesium sulfate, and then the magnesium sulfate was filtered off as a slurry using a silica gel bed. After removing the ethyl acetate under reduced pressure, the residue was purified by silica gel chromatography using n-heptane / ethyl acetate (1:2 v / v). Yield: 9.7 g (45 mmol), 45%. Purity: According to 1 The H NMR is approximately 98%.

[0385] Example B9:

[0386]

[0387] A mixture of 25.1 g (100 mmol) of 2,5-dibromo-4-methylpyridine [3430-26-0], 15.6 g (100 mmol) of 4-chlorophenylboronic acid [1679-18-1], 27.6 g (200 mmol) of potassium carbonate, 1.57 g (6 mmol) of triphenylphosphine [603-35-0], 676 mg (3 mmol) of palladium(II) acetate [3375-31-3], 200 g of glass beads (3 mm in diameter), 200 ml of acetonitrile, and 100 ml of ethanol was heated under reflux for 48 hours. After cooling, the solvent was removed under reduced pressure, and 500 ml of toluene was added. The mixture was washed twice with 300 ml of water and once with 200 ml of saturated sodium chloride solution. After drying with magnesium sulfate, the mixture was filtered through a silica gel bed in slurry form and washed with 300 ml of toluene. After removing toluene under reduced pressure, the mixture was recrystallized once from methanol / ethanol (1:1 v / v) and once from n-heptane. Yield: 17.3 g (61 mmol), 61%. Purity: according to...1 The H NMR value is approximately 95%.

[0388] Example B10:

[0389]

[0390] B10 can be prepared similarly to the procedure described with respect to Example B9. For this purpose, 4-bromo-6-tert-butylpyrimidine [19136-36-8] is used instead of 2,5-dibromo-4-methylpyridine. Yield: 70%.

[0391] Example B11:

[0392]

[0393] A mixture of 28.3 g (100 mmol) of B9, 12.8 g (105 mmol) of phenylboronic acid, 31.8 g (300 mmol) of sodium carbonate, 787 mg (3 mmol) of triphenylphosphine, 225 mg (1 mmol) of palladium(II) acetate, 300 mL of toluene, 150 mL of ethanol, and 300 mL of water was heated under reflux for 48 hours. After cooling, the mixture was expanded with 300 mL of toluene, and the organic phase was removed, washed once with 300 mL of water and once with 200 mL of saturated sodium chloride solution, and dried over magnesium sulfate. After solvent removal, the residue was purified by silica gel chromatography (toluene / ethyl acetate, 9:1 v / v). Yield: 17.1 g (61 mmol), 61%. Purity: according to 1 The H NMR value is approximately 97%.

[0394] The following compounds can be synthesized in a similar manner:

[0395]

[0396]

[0397] Example B15:

[0398]

[0399] A mixture of 164.2 g (500 mmol) of 2-(1,1,2,2,3,3-hexamethylindan-5-yl)-4,4,5,5-tetramethyl-[1,3,2]dioxane[152418-16-9] (boric acid can be used similarly), 142.0 g (500 mmol) of 5-bromo-2-iodopyridine[223463-13-6], 159.0 g (1.5 mol) of sodium carbonate, 5.8 g (5 mmol) of tetrakis(triphenylphosphine)palladium(0), 700 ml of toluene, 300 ml of ethanol, and 700 ml of water was refluxed for 16 hours with good stirring. After cooling, 1000 ml of toluene was added, the organic phase was removed, and the aqueous phase was extracted again with 300 ml of toluene. The combined organic phases were washed once with 500 ml of saturated sodium chloride solution. The organic phase was dried over sodium sulfate and the solvent was removed under reduced pressure. The crude product was then recrystallized twice from approximately 300 ml of EtOH. Yield: 130.8 g (365 mmol), 73%. Purity: According to... 1 The H NMR value is approximately 95%.

[0400] The following compounds can be prepared similarly. The pyridine derivatives used here are typically 5-bromo-2-iodopyridine ([223463-13-6]), which is not listed separately in the table below; only the different pyridine derivatives are explicitly listed in the table. Recrystallization can be achieved using solvents such as ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol, or methanol. These solvents can also be used for thermal extraction, or for purification by silica gel chromatography in an automated column system (Torrent from Axel Semrau).

[0401]

[0402]

[0403]

[0404] Example B24:

[0405] Variant A:

[0406]

[0407] The following ingredients were added: 35.8 g (100 mmol) of B15, 25.4 g (100 mmol) of bis(pinacolyl)diborane [73183-34-3], 49.1 g (500 mmol) of potassium acetate, 1.5 g (2 mmol) of 1,1-bis(diphenylphosphino)ferrocene palladium(II) dichloride complex with DCM [95464-05-4], 200 g of glass beads (3 mm in diameter), and 700 ml of 1,4-diphenylphosphinosulfonate. A mixture of alkylene and 700 ml toluene was heated under reflux for 16 hours. After cooling, the suspension was filtered through a diatomaceous earth bed and the solvent was removed under reduced pressure. The black residue was dissolved in 1000 ml of hot n-heptane, cyclohexane, or toluene and filtered hot through a diatomaceous earth bed, then concentrated to approximately 200 ml, during which time the product began to crystallize. Alternatively, hot extraction with ethyl acetate could be used. Crystallization was completed overnight in a refrigerator, the crystals were filtered off and washed with a small amount of n-heptane. A second product fraction could be obtained from the mother liquor. Yield: 31.6 g (78 mmol), 78%. Purity: according to 1 The H NMR value is approximately 95%.

[0408] Variant B: Transformation of aryl chlorides

[0409] For example, in the preparation of variant A, the difference is that 2 mmol of SPhos [657408-07-6] and 1 mmol of palladium(II) acetate are used instead of the complex of 1,1-bis(diphenylphosphino)-ferrocene palladium(II) dichloride with DCM.

[0410] The following compounds can be prepared in a similar manner, and purification can also be performed using cyclohexane, toluene, acetonitrile, or a mixture of the solvents mentioned above instead of n-heptane:

[0411]

[0412]

[0413]

[0414]

[0415]

[0416]

[0417] Example B56:

[0418]

[0419] A mixture of 28.1 g (100 mmol) of B25, 28.2 g (100 mmol) of 1-bromo-2-iodobenzene [583-55-1], 31.8 g (300 mmol) of sodium carbonate, 787 mg (3 mmol) of triphenylphosphine, 225 mg (1 mmol) of palladium(II) acetate, 300 mL of toluene, 150 mL of ethanol, and 300 mL of water was heated under reflux for 24 hours. After cooling, the mixture was expanded with 500 mL of toluene, and the organic phase was removed, washed once with 500 mL of water and once with 500 mL of saturated sodium chloride solution, and dried over magnesium sulfate. After solvent removal, the residue was recrystallized from ethyl acetate / n-heptane or purified by silica gel chromatography (toluene / ethyl acetate, 9:1 v / v). Yield: 22.7 g (73 mmol), 73%. Purity: according to 1 The H NMR value is approximately 97%.

[0420] The following compounds can be prepared in a similar manner, and recrystallization can be achieved using solvents such as ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol, or methanol. These solvents can also be used for thermal extraction, or for purification by silica gel chromatography on an automated column system (Torrent from Axel Semrau).

[0421]

[0422]

[0423]

[0424]

[0425] Example B81:

[0426]

[0427] A mixture of 36.4 g (100 mmol) of 2,2'-(5-chloro-1,3-phenyleneyl)bis[4,4,5,5-tetramethyl-1,3,2-dioxane][1417036-49-7], 65.2 g (210 mmol) of B56, 42.4 g (400 mmol) of sodium carbonate, 1.57 g (6 mmol) of triphenylphosphine, 500 mg (2 mmol) of palladium(II) acetate, 500 mL of toluene, 200 mL of ethanol, and 500 mL of water was heated under reflux for 48 hours. After cooling, the mixture was expanded with 500 mL of toluene, and the organic phase was removed, washed once with 500 mL of water and once with 500 mL of saturated sodium chloride solution, and dried over magnesium sulfate. After solvent removal, the residue was purified by silica gel chromatography (n-heptane / ethyl acetate, 2:1 v / v). Yield: 41.4 g (68 mmol), 68%. Purity: According to... 1 The H NMR value is approximately 95%.

[0428] The following compounds can be prepared in a similar manner, and recrystallization can be achieved using solvents such as ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol, or methanol. These solvents can also be used for thermal extraction, or for purification by silica gel chromatography on an automated column system (Torrent from Axel Semrau).

[0429]

[0430]

[0431]

[0432]

[0433] Example B93:

[0434]

[0435] A mixture of 17.1 g (100 mmol) of 4-(2-pyridyl)phenol [51035-40-6] and 12.9 g (100 mmol) of diisopropylethylamine [7087-68-5] was stirred in 400 mL of dichloromethane for 10 minutes at room temperature. 6.2 mL (40 mmol) of 5-chloroisophthaloyl chloride [2855-02-9] dissolved in 30 mL of dichloromethane was added dropwise, and the reaction mixture was stirred at room temperature for 14 hours. Subsequently, 10 mL of water was added dropwise, and the reaction mixture was transferred to a separatory funnel. The organic phase was washed twice with 100 mL of water and once with 50 mL of saturated NaCl solution, dried over sodium sulfate, and concentrated to dryness. Yield: 18.0 g (38 mmol), 95%. Purity: According to1 The H NMR value is approximately 95%.

[0436] The following compounds can be prepared in a similar manner; if the molar amounts of reactants used differ from those described in the procedure for B93, specify the molar amounts of reactants used.

[0437]

[0438]

[0439] Example B101:

[0440]

[0441] 2.0 g (50 mmol) of sodium hydride (60% dispersion in paraffin oil) [7646-69-7] was suspended in 300 ml of THF, then 5.0 g (10 mmol) of B95 was added, and the suspension was stirred at room temperature for 30 minutes. Subsequently, 1.2 ml of iodomethane (50 mmol) [74-88-4] was added, and the reaction mixture was stirred at room temperature for 50 hours. 20 ml of concentrated ammonia solution was added, the mixture was stirred for another 30 minutes, and most of the solvent was removed under reduced pressure. The residue was dissolved in 300 ml of dichloromethane, washed once with 200 ml of 5% ammonia solution, twice with 100 ml of water each time, and once with 100 ml of saturated sodium chloride solution, and then dried over magnesium sulfate. Dichloromethane was removed under reduced pressure, and the crude product was recrystallized from ethyl acetate / methanol. Yield: 4.3 g (8 mmol), 80%. Purity: according to 1 The H-NMR value is approximately 98%.

[0442] The following compounds can be prepared in a similar manner:

[0443]

[0444]

[0445] Example B105:

[0446]

[0447] A mixture of 36.4 g (100 mmol) of 2,2'-(5-chloro-1,3-phenyleneyl)bis[4,4,5,5-tetramethyl-1,3,2-dioxane][1417036-49-7], 70.6 g (210 mmol) of B69, 42.4 g (400 mmol) of sodium carbonate, 2.3 g (2 mmol) of tetra(triphenylphosphine)palladium(O), 1000 ml of 1,2-dimethoxyethane, and 500 ml of water was heated under reflux for 48 hours. After cooling, the precipitated solid was filtered off and washed twice with 20 ml of ethanol. The solid was dissolved in 500 ml of dichloromethane and filtered through a diatomaceous earth bed. The filtrate was concentrated to 100 ml, then 400 ml of ethanol was added, and the precipitated solid was filtered off. The crude product was recrystallized once from ethyl acetate. Yield: 43.6 g (70 mmol), 70%. Purity: based on... 1 The H NMR value is approximately 96%.

[0448] The following compounds can be prepared in a similar manner, and recrystallization can be achieved using solvents such as ethyl acetate, cyclohexane, toluene, acetonitrile, n-heptane, ethanol, or methanol. These solvents can also be used for thermal extraction, or for purification by silica gel chromatography on an automated column system (Torrent from Axel Semrau).

[0449]

[0450]

[0451]

[0452] Example B119

[0453]

[0454] Under stirring, 57.1 g (100 mmol) of B81, 25.4 g (100 mmol) of bis(pinacolyl)diborane [73183-34-3], 49.1 g (500 mmol) of potassium acetate, 2 mmol of SPhos [657408-07-6], 1 mmol of palladium(II) acetate, 200 g of glass beads (3 mm in diameter) and 700 ml of 1,4-dioxane were added. The mixture of alkanes was heated to reflux for 16 hours. After cooling, the suspension was filtered through a diatomaceous earth bed, and the solvent was removed under reduced pressure. The black residue was dissolved in 1000 ml of hot ethyl acetate and filtered hot through a diatomaceous earth bed, then concentrated to approximately 200 ml, during which time the product began to crystallize. Crystallization was completed overnight in a refrigerator, the crystals were filtered off and washed with a small amount of ethyl acetate. A second product fraction could be obtained from the mother liquor. Yield: 31.6 g (78 mmol), 78%. Purity: according to 1 The H-NMR value is approximately 95%.

[0455] The following compounds can be prepared in a similar manner, and toluene, n-heptane, cyclohexane, dichloromethane, or acetonitrile can be used instead of ethyl acetate for recrystallization or for hot extraction under slightly soluble conditions:

[0456]

[0457]

[0458]

[0459]

[0460]

[0461]

[0462]

[0463]

[0464] Example B152:

[0465]

[0466] Prepared according to G. Markopoulos et al., Angew. Chem. Int. Ed. (International Edition of Applied Chemistry), 2012, 51, 12884.

[0467] b)

[0468]

[0469] According to the procedure of JP 2000-169400. 5.7 g [105 mmol] of sodium methoxide was added in portions to a solution of 36.6 g (100 mmol) of 1,3-bis(2-bromophenyl)-2-propen-1-one [126824-93-9] (stage a) in 300 mL of anhydrous acetone, and the mixture was stirred at 40 °C for 12 hours. The solvent was removed under reduced pressure, and the residue was dissolved in ethyl acetate, washed three times with 200 mL of water each time and twice with 200 mL of saturated sodium chloride solution each time, and dried over magnesium sulfate. The oily substance obtained after solvent removal under reduced pressure was subjected to rapid chromatography (Torrent CombiFlash, from Axel Semrau). Yield: 17.9 g (44 mmol), 44%. Purity: according to 1 The H NMR value is approximately 97%.

[0470] c)

[0471]

[0472] 2.4 g (2.4 mmol) of anhydrous copper chloride (I) [7758-89-6] was added to a solution of 200 mmol of 2-chlorophenyl magnesium bromide [36692-27-0] in 200 mL of di-n-butyl ether at 0 °C, and the mixture was stirred for another 30 min. Then, 40.6 g (100 mmol) of the product of stage b) in 200 mL of toluene was added dropwise over a 30-minute period, and the mixture was stirred at 0 °C for another 5 h. The reaction mixture was quenched by carefully adding 100 mL of water and 220 mL of 1 N hydrochloric acid sequentially. The organic phase was separated, washed twice with 200 mL of water each time, once with 200 mL of saturated sodium bicarbonate solution, and once with 200 mL of saturated sodium chloride solution, and dried over magnesium sulfate. The resulting oily substance, after solvent removal under reduced pressure, was filtered through silica gel into toluene. The crude product thus obtained could be further converted without further purification. Yield: 49.8 g (96 mmol), 96%. Purity: According to 1 The H NMR value is approximately 90-95%.

[0473] d)

[0474]

[0475] To a solution of 51.9 g (100 mmol) of stage c) product cooled to 0 °C in 500 mL of dichloromethane (DCM), 1.0 mL of trifluoromethanesulfonic acid was added, followed by the addition of 50 g of phosphorus pentoxide in multiple portions. The mixture was heated to room temperature and stirred for 2 hours. Phosphorus pentoxide was decanted and suspended in 200 mL of DCM, and then decanted again. The combined DCM phases were washed twice with water and once with saturated sodium chloride solution, and dried over magnesium sulfate. The waxy residue obtained after solvent removal under reduced pressure was subjected to rapid chromatography (Torrent CombiFlash, from Axel Semrau). Yield: 31.5 g (63 mmol), 63%, mixture of isomers. Purity: according to 1 The H NMR value is approximately 90-95%.

[0476] e)

[0477]

[0478] A mixture of 25.0 g (50 mmol) of stage d) product, 2 g of Pd / C (10%), 200 mL of methanol, and 300 mL of ethyl acetate was contacted with 3 bar of hydrogen in a stirred autoclave and hydrogenated at 30 °C until hydrogen absorption was complete. The mixture was filtered through a diatomaceous earth bed as an ethyl acetate slurry, and the filtrate was concentrated to dryness. The resulting oil was subjected to rapid chromatography (Torrent CombiFlash, from Axel Semrau). Yield: 17.2 g (34 mmol), 68%. Purity: according to 1 The H NMR is approximately 95% (cis,cis isomer).

[0479] The following compounds can be prepared in a similar manner:

[0480]

[0481]

[0482] Example B156:

[0483]

[0484] 54.5 g (100 mmol) of B152, 59.0 g (210 mmol) of 2-phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaneborane-2-yl)pyridine [879291-27-7], 127.4 g (600 mmol) of tripotassium phosphate, 1.57 g (6 mmol) of triphenylphosphine, and 449 mg (2 mmol) of palladium(II) acetate were added to 750 ml of toluene and 300 ml of dimethyl ether. The mixture of alkane and 500 ml of water was heated under reflux for 30 hours. After cooling, the organic phase was separated, washed twice with 300 ml of water and once with 300 ml of saturated sodium chloride solution, and dried over magnesium sulfate. Magnesium sulfate was filtered through a diatomaceous earth bed as a toluene slurry, the filtrate was concentrated to dryness under reduced pressure, and the remaining foamy residue was recrystallized from acetonitrile / ethyl acetate. Yield: 41.8 g (64 mmol), 64%. Purity: according to 1 The H NMR value is approximately 95%.

[0485] The following compounds can be prepared in a similar manner:

[0486]

[0487]

[0488] B: Ligand synthesis:

[0489] Example L1:

[0490] Variant A:

[0491]

[0492] A mixture of 7.0 g (15 mmol) B3, 19.9 g (30.0 mmol) B120, 9.5 g (90 mmol) sodium carbonate, 340 mg (1.3 mmol) triphenylphosphine, 98 mg (0.44 mmol) palladium(II) acetate, 200 mL toluene, 100 mL ethanol, and 200 mL water was heated under reflux for 40 hours. After cooling, the precipitated solid was filtered off and washed twice with 30 mL of ethanol each time. The crude product was dissolved in 300 mL of dichloromethane and filtered through a silica gel bed. The silica gel bed was washed three times each with 200 mL of dichloromethane / ethyl acetate at a 1:1 ratio. The filtrate was washed twice with water and once with saturated sodium chloride solution and dried over sodium sulfate. The filtrate was concentrated to dryness. The residue was purified chromatographically on silica gel using an ethyl acetate / heptane eluent mixture (from an automated rapid column system of Axel Semrau). Yield: 10.7 g (7.8 mmol), 52%. Purity: According to 1 The H NMR is approximately 98%.

[0493] Variant B:

[0494] A mixture of 5.7 g (15 mmol) of B5, 19.9 g (30.0 mmol) of B120, 13.8 g (60 mmol) of potassium phosphate monohydrate, 507 mg (0.6 mmol) of third-generation Xphos cyclopalladium [1445085-55-1], 200 mL of THF, and 100 mL of water was heated under reflux for 20 hours. After cooling, the precipitated solid was filtered off and washed twice with 30 mL of water and twice with 30 mL of ethanol each time. Purification was achieved as described in variant A. Yield: 13.2 g (9.6 mmol), 64%. Purity: according to 1 The H NMR value is approximately 99%.

[0495] The following compounds can be prepared using a procedure similar to that described for L1 (variant A or B). In this case, toluene, cyclohexane, ethyl acetate, or dimethylformamide can also be used for purification by recrystallization or thermal extraction. Alternatively, the ligands can be purified by chromatography.

[0496]

[0497]

[0498]

[0499]

[0500]

[0501]

[0502]

[0503]

[0504]

[0505]

[0506] C: Synthesis of metal complexes:

[0507] Variant A: Complexes with C–N– or C–O– donor sets of the I1-Ir2(L1) and I2-Ir2(L1) types.

[0508]

[0509] Initially, a mixture of 13.8 g (10 mmol) of ligand L1, 9.8 g (20 mmol) of iridium(III) triacetylacetone [15635-87-7], and 100 g of hydroquinone [123-31-9] was placed in a 1000 ml double-necked round-bottom flask with a glass-coated magnetic stir bar. The flask had a water separator (for media with a density less than water) and an air condenser covered with argon gas, and was placed in a metal heating bath. The apparatus was purged from above with argon gas for 15 minutes via the argon-covered system, allowing argon to flow out from the side neck of the double-necked flask. A glass-coated Pt-100 thermocouple was introduced into the flask through the side neck, with its end positioned directly above the magnetic stir bar. The apparatus was then insulated with several loose turns of household aluminum foil, extending to the middle of the riser tube of the water separator. The apparatus was then rapidly heated to 250°C using a heated laboratory stirring system, and the temperature was measured using a Pt-100 thermal sensor immersed in the molten stirred reaction mixture. The reaction mixture was maintained at 250°C for the next 2 hours, during which a small amount of condensate was distilled off and collected in a water separator. The reaction mixture was cooled to 190°C, and then 100 ml of ethylene glycol was added dropwise. The mixture was further cooled to 80°C, and then 500 ml of methanol was added dropwise; the mixture was then heated under reflux for 1 hour. The resulting suspension was filtered through a double-ended glass frit filter, and the solid was washed twice with 50 ml of methanol and then dried under reduced pressure. The resulting solid was dissolved in 200 ml of dichloromethane and filtered through approximately 1 kg of silica gel (column diameter approximately 18 cm) in the dark under evacuated air, leaving a dark fraction at the beginning. The core fraction was cut off and concentrated on a rotary evaporator while MeOH was continuously added dropwise until crystallization. After removal by suction, the mixture was washed with a small amount of MeOH and dried under reduced pressure to achieve further purification of the diastereomeric product mixture.

[0510] A mixture of diastereomeric metal complexes containing ΔΔ and ΛΛ isomers (racemic) and ΛΔ isomers (meta-racemic), and a small proportion of other meridional isomers, was dissolved in 300 mL of dichloromethane, poured onto 100 g silica gel, and separated chromatographically using a silica gel column (approximately 1.7 kg of silica gel) in the form of a toluene slurry. The eluent used was initially toluene, followed by toluene containing a small proportion of ethyl acetate. 5.1 g of the earlier eluted isomer, hereinafter referred to as isomer 1 (I1), and 5.3 g of the later eluted isomer, hereinafter referred to as isomer 2 (I2), were obtained. Under careful purging of air and protection from light, isomers 1 (I1) and 2 (I2) were further purified four times, separately, by thermal extraction with n-butyl acetate (for isomer 1) and toluene (for isomer 2) (initial loading was approximately 150 ml in each case; extraction sleeve: standard Soxhlett sleeve made of cellulose from Whatman). Finally, the products were heat-treated at 280 °C under high vacuum. Yield: Isomer 1 (I1) 3.7 g red solid (2.1 mmol), 21%, based on the amount of ligand used. Purity: >99.7% according to HPLC; Isomer 2 (I2) 3.7 g red solid (2.1 mmol), 21%, based on the amount of ligand used. Purity: 99.8% according to HPLC. Finally, the products were heat-treated at 250 °C under high vacuum (10 -6 The metal complex was heat-treated at a temperature of 1000 mbar.

[0511] The reported yields of isomer 1 (I1) or isomer 2 (I2) are always based on the amount of ligand used.

[0512] The images of the complexes shown below always show only one isomer. Mixtures of isomers can be separated, but can also be used as isomer mixtures in OLED devices. The metal complexes shown below can, in principle, be purified by chromatography (typically using an automated column system (Torrent from Axel Semrau)), recrystallization, or thermal extraction. Residual solvents can be removed by heat treatment under high vacuum at typically 250–330 °C. The following compounds can be synthesized similarly. Reaction conditions are illustrated using isomer 1 (I1) as an example. Chromatographic separation of the diastereomeric mixtures typically obtained is achieved on rapid silica gel in an automated column system (Torrent from Axel Semrau).

[0513] Similarly, by sequentially adding the first 10 mmol of Ir(acac)3 and reacting at 250 °C for 1 hour, then adding 10 mmol of Rh(acac)3[14284-92-5] and further reacting at 250 °C for 1 hour, followed by processing and purification as described above, a mixed metal Rh-Ir complex can be obtained.

[0514] Variant B: A carbene complex with a C–C–donor group.

[0515] 10 mmol carbene ligand and 40 mmol Ag2O were mixed in 300 ml of a solution. The suspension in the alkane was stirred at 30°C for 12 hours. Then 20 mmol of [Ir(COD)Cl]2[12112-67-3] was added and the mixture was heated under reflux for 12 hours. The solid was filtered off while the mixture was hot, and then 50 ml of hot distillate was used each time. The product was washed three times with alkylene, and the filtrates were combined and concentrated to dryness under reduced pressure. The crude product obtained was separated twice by chromatographic separation on basic alumina with ethyl acetate / cyclohexane or toluene. The product was further purified by five consecutive hot extractions with acetonitrile and two hot extractions with ethyl acetate / acetonitrile under careful removal of air and protection from light (the initial loading volume was approximately 200 ml in each case; extraction sleeves: standard Soxhlett sleeves made of cellulose from Whatman). Finally, the product was sublimated or heat-treated under high vacuum. Purity: >99.8% according to HPLC.

[0516]

[0517]

[0518]

[0519]

[0520]

[0521]

[0522]

[0523]

[0524]

[0525]

[0526]

[0527]

[0528]

[0529]

[0530]

[0531] D: Functionalization of metal complexes:

[0532] 1) Halogenation of iridium complexes:

[0533] At -30 to +30 °C, in darkness and under vented air, 10 mmol of a complex containing an A×CH group (where A = 1–4) at the para-position of iridium in the bidentate subligand was added to a solution or suspension (depending on the solubility of the metal complex) in 500 to 2000 ml of dichloromethane, along with A×10.5 mmol of N-halosuccinimide (halogen: Cl, Br, I), and the mixture was stirred for 20 hours. Complexes slightly soluble in DCM can also be converted in other solvents (TCE, THF, DMF, chlorobenzene, etc.) and at high temperatures. Subsequently, the solvent was substantially removed under reduced pressure. The residue was extracted by boiling with 100 ml of methanol, and the solid was filtered off, washed three times with 30 ml of methanol, and then dried under reduced pressure. This yields an iridium complex brominated / halogenated at the para-position of iridium. Complexes with HOMO(CV) values ​​of approximately -5.1 to -5.0 eV and smaller exhibit an oxidation tendency (Ir(III) → Ir(IV)), with the oxidant being bromine released from NBS. This oxidation reaction is readily apparent through a noticeable green or brown discoloration of the originally yellow to red solution / suspension of the luminescent material. In these cases, an additional 1–2 equivalents of NBS are added. For post-treatment, 300–500 ml of methanol and 4 ml of hydrazine hydrate are added as a reducing agent, which causes the green or brown solution / suspension to turn yellow or red (reduction of Ir(IV) → Ir(III)). The solvent is then substantially removed under reduced pressure, 300 ml of methanol is added, and the solid is filtered off, washed three times with 100 ml of methanol each time, and dried under reduced pressure.

[0534] Substoichiometric bromination of complexes with four CH groups at the para-position of the iridium atom, such as monobromination and dibromination, is generally carried out with less selectivity compared to stoichiometric bromination. The crude products of these brominations can be separated by chromatography (from A. Semrau's CombiFlash Torrent).

[0535] Synthesis of Ir2(L1-4Br):

[0536]

[0537] 5.0 g (45 mmol) of N-bromosuccinimide was added in a single addition to a suspension of 17.6 g (10 mmol) of I1-Ir2 (L1) in 2000 mL of DCM, and the mixture was stirred at room temperature for 20 hours. Then, 2 mL of hydrazine hydrate and 300 mL of MeOH were added sequentially. After removing approximately 1900 mL of DCM under reduced pressure, the red solid was filtered off, washed three times with approximately 50 mL of methanol, and then dried under reduced pressure. Yield: 18.6 g (9.0 mmol), 90%; Purity: >98.0% according to NMR.

[0538] The following compounds can be synthesized in a similar manner:

[0539]

[0540]

[0541]

[0542] 2) Suzuki coupling with iridium bromide complexes:

[0543] Variant A, biphasic reaction mixture:

[0544] Add 10 mmol of the bromide complex, 12-20 mmol of boric acid or borate ester (for each Br functional group) and 60-100 mmol of tripotassium phosphate to 300 ml of toluene and 100 ml of dimethyl sulfoxide. 0.6 mmol of tri-o-tolylphosphine and 0.1 mmol of palladium(II) acetate were added sequentially to a suspension of a mixture of alkylene and 300 mL of water, and the mixture was heated under reflux for 16 hours. After cooling, 500 mL of water and 200 mL of toluene were added to remove the aqueous phase, and the organic phase was washed three times with 200 mL of water and once with 200 mL of saturated sodium chloride solution, and dried over magnesium sulfate. The mixture was filtered through a diatomaceous earth bed and washed with toluene, and toluene was almost completely removed under reduced pressure. 300 mL of methanol was added, and the precipitated crude product was filtered off, washed three times with 50 mL of methanol each time, and dried under reduced pressure. The crude product was purified by silica gel chromatography in an automated column system (Torrent from Semrau). Subsequently, it was purified by chromatography using ethyl acetate, toluene, diethyl ether, and other solvents. The complex can be further purified by thermal extraction in solvents such as alkanes, acetonitrile, cyclohexane, o-xylene or p-xylene, n-butyl acetate, etc. Alternatively, it can be recrystallized from these solvents and high-boiling-point substances such as dimethylformamide, dimethyl sulfoxide, or mesitylene. Finally, the metal complex is heat-treated under high vacuum (p = approximately 10). -6 Heat treatment is achieved at a temperature range of approximately 200-300°C under millibars.

[0545] Variant B, single-phase reaction mixture:

[0546] Add 10 mmol of the bromide complex, 12-20 mmol of boric acid or borate ester (for each Br functional group), 100-180 mmol of base (potassium fluoride, tripotassium phosphate (anhydrous, monohydrate, or trihydrate), potassium carbonate, cesium carbonate, etc.), and 50 g of glass beads (3 mm in diameter) to 100-500 ml of aprotic solvent (THF, dioxin, dioxin). 0.2 mmol of tetra(triphenylphosphine)palladium(O)[14221-01-3] was added to a suspension of Pd(OAc)2 (such as alkylene, xylene, mesitylene, dimethylacetamide, NMP, DMSO, etc.), and the mixture was heated under reflux for 24 hours. Alternatively, other phosphines in combination with Pd(OAc)2, such as triphenylphosphine, tri-tert-butylphosphine, SPhos, XPhos, RuPhos, XanthPhos, etc., were used, in which case the preferred phosphine:palladium ratio was 3:1 to 1.2:1. The solvent was removed under reduced pressure, the product was dissolved in a suitable solvent (toluene, dichloromethane, ethyl acetate, etc.), and purification was achieved as described in variant A.

[0547] Synthesis of Ir2100:

[0548]

[0549] Variant B:

[0550] The solution was prepared using 20.7 g (10.0 mmol) of I1-Ir(L1-4Br), 9.75 g (80.0 mmol) of phenylboronic acid [98-80-6], 27.6 g (120 mmol) of tripotassium phosphate monohydrate, 116 mg (0.1 mmol) of tetrakis(triphenylphosphine)palladium(O), and 500 mL of anhydrous dimethyl sulfoxide, at 100 °C for 16 hours. Separation was performed by silica gel chromatography with toluene / heptane (automated column system, Torrent from Axel Semirau), followed by five thermal extractions with toluene. Yield: 9.5 g (5.6 mmol), 46%; Purity: approximately 99.8% according to HPLC.

[0551] The following compounds can be prepared in a similar manner:

[0552]

[0553]

[0554]

[0555]

[0556] 3) Deuteration of Ir complexes

[0557] Example: Ir2(L7-D12)

[0558]

[0559] A mixture of 1 mmol Ir2 (L7), 1 mmol sodium ethoxide, 5 mL methanol-D4, and 80 mL DMSO-D6 was heated to 120 °C for 2 hours. After cooling to 50 °C, 1 mL of DCl (10% aqueous solution) was added. The solvent was removed under reduced pressure, and the residue was purified by DCM chromatography on silica gel. Yield: 0.95 mmol, 95%, deuteration level >95%.

[0560] In a similar manner, compounds Ir2(L11), Ir2(L12), and Ir2(L20) can be tetradeuterated:

[0561] Device Examples:

[0562] OLED manufacturing

[0563] The complexes of this invention can be processed from solution, resulting in OLEDs with good performance that are easier to manufacture compared to vacuum-processed OLEDs. The manufacture of fully solution-based OLEDs has been described numerous times in the literature, for example in WO 2004 / 037887. The manufacture of vacuum-based OLEDs has also been described numerous times previously, including in WO 2004 / 058911. In the embodiments discussed below, layers applied in a solution-based and vacuum-based manner are combined within the OLED, such that processing up to and including the light-emitting layer is achieved from solution, and subsequent layers (hole-blocking layer and electron-transporting layer) are processed from vacuum. For this purpose, the previously described general method is matched and combined with the situation described herein (layer thickness variation, materials) as follows. The general structure is as follows: substrate / ITO (50 nm) / hole injection layer (HIL) / hole transport layer (HTL) / light-emitting layer (EML) / hole-blocking layer (HBL) / electron transport layer (ETL) / cathode (aluminum, 100 nm). The substrate used was a glass plate coated with a 50 nm thick structured ITO (indium tin oxide). For better handling, these were coated with PEDOT:PSS (poly(3,4-ethylenedioxy-2,5-thiophene) polystyrene sulfonate, purchased from Heraeus Precious Metals GmbH & Co. KG, Germany). PEDOT:PSS was spin-coated from water in air and subsequently baked in air at 180°C for 10 minutes to remove residual water. A hole transport layer and a light-emitting layer were then applied to these coated glass plates. The hole transport layer used was crosslinkable. A polymer with the structure shown below was used, which could be synthesized according to WO 2010 / 097155 or WO 2013 / 156130.

[0564]

[0565] The hole-transporting polymer is dissolved in toluene. The typical solids content of this solution is approximately 5 g / L, and a typical layer thickness of 20 nm is achieved here via spin coating. The layer is spin-coated in an inert gas atmosphere (argon in this example) and baked at 180°C for 60 minutes.

[0566] The light-emitting layer always comprises at least one matrix material (host material) and a light-emitting dopant (light emitter). Alternatively, mixtures of various matrix materials and co-dopersies may be present. Details given here, such as TMM-A (92%): dopant (8%), indicate that material TMM-A is present in the light-emitting layer at a weight percentage of 92%, and the dopant is present in the light-emitting layer at a weight percentage of 8%. The mixture used for the light-emitting layer is dissolved in toluene or optionally chlorobenzene. A typical solids content of this solution is approximately 17 g / L, and a typical layer thickness of 60 nm is achieved here by spin coating. The layer is spin-coated in an inert gas atmosphere (argon in this example) and baked at 150 °C for 10 minutes. The materials used in this example are shown in Table 1.

[0567] Table 1: EML materials used

[0568]

[0569] The materials used for the hole-blocking layer and the electron transport layer are applied by thermal vapor deposition in a vacuum chamber. The electron transport layer may, for example, consist of more than one material, which is mixed with each other in a specific volume ratio by co-evaporation. Details given here, such as ETM1:ETM2 (50%:50%), refer to the fact that ETM1 and ETM2 materials are present in the layer at a 50% volume ratio, respectively. The materials used in this example are shown in Table 2.

[0570] Table 2: HBL and ETL materials used

[0571]

[0572] The cathode was formed by thermal evaporation of a 100 nm aluminum layer. The OLED was characterized using standard methods. The EML mixtures and structures of the studied OLED components are shown in Tables 3 and 4. The corresponding results are shown in Table 5.

[0573] Table 3: EML mixtures of the studied OLED components

[0574]

[0575]

[0576] Table 4: Structure of the studied OLED components

[0577]

[0578] Table 5: Results of solution-treated OLEDs (at 1000 cd / m²) 2 (Measured under brightness)

[0579]

[0580] Similar to Example E-4 (Table 3), the compounds of the present invention listed below can be used to fabricate OLED devices: I1-Rh2(L1), I2-Rh2(L1), I1-Ir2(L2), I2-Ir2(L2), I1-Ir2(L3), I2-Ir2(L3), I1-Ir2(L4), I2-Ir2(L4), I1-Ir2(L5), I2-Ir2(L5), I1-Ir2(L6), I2-Ir2(L6), I1 -Ir2(L7), I2-Ir2(L7), I1-Ir2(L8), I2-Ir2(L8), I1-Ir2(L9), I2-Ir2(L9), I1-Ir2(L10), I2-Ir2(L10 ), Ir2(L11), Ir2(L12), I1-Ir2(L13), I2-Ir2(L13), I1-Ir2(L14), I2-Ir2(L14), I1-Ir2(L15), I2-Ir2 (L15), I1-Ir2(L16), I2-Ir2(L16), I1-Ir2(L17), I2-Ir2(L17), I1-Ir2(L18), I2-Ir2(L18), I2-Ir2(L 19), Ir2(L20), I1-Ir2(L21), I2-Ir2(L21), I1-Ir2(L22), I2-Ir2(L22), I1-Ir2(L23), I2-Ir2(L23), I 1-Ir2(L24), I2-Ir2(L24), I1Ir2(L25), I2-Ir2(L25), I1-Ir2(L26), I2-Ir2(L26), I1-Ir2(L27), I2-I r2(L27), Ir2(L28), Ir2(L29), Ir2(L7-D12), Ir2101, Rh2100, Ir2102, Ir2103, Ir2105, Ir2106, Ir2107.

[0581] These OLED devices exhibit strong and long-lasting yellow to red electroluminescence.

Claims

1. A compound of formula (1a') or (1b') The R groups explicitly shown therein may be the same or different in each case and are selected from H, D, F, CH3, and CD3, and other symbols used therein are as follows: M is iridium; V is a group of formula (5a'''). One of the dashed bonds represents a bond connected to the corresponding six-membered aryl or heteroaryl group shown in formula (1a') or (1b'), and the other two dashed bonds each represent a bond connected to the subligand L. L is a bidentate monoanion subligand selected from the structure of formula (L-2-1a). The symbols used have the definitions given above, and "o" represents the position where the subligand L is linked to the group of formula (5a''').

2. A method for preparing the compound of claim 1, said method comprising reacting a ligand with an iridium reactant selected from a metal alkoxide of formula (57), a metal ketone of formula (58), a metal halide of formula (59), or a metal carboxylate of formula (60): Where M is iridium, Hal = F, Cl, Br or I, and R is the same or different in each case and is selected from H, D, CH3 and CD3, or the iridium reactant is in the form of a hydrate.

3. A formulation comprising at least one compound of claim 1 and at least one solvent.

4. Use of the compound of claim 1 in an electronic device.

5. An electronic device comprising at least one compound according to claim 1.

6. The electronic device according to claim 5, wherein the electronic device is an organic electroluminescent device, and wherein the compound according to claim 1 is present as a luminescent compound in one or more luminescent layers.

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