METAL COMPLEX

Description

FIELD

[0001] The present invention relates to iridium complexes suitable for use in organic electroluminescent devices, particularly as emitters.BACKGROUND

[0002] According to the prior art, in phosphorescent organic electroluminescent devices (OLEDs), mainly bis- and tris-ortho-metalated iridium complexes with aromatic ligands are used as triplet emitters, the ligands having a negatively charged carbon atom and a neutral nitrogen atom. Examples of such complexes are tris(phenylpyridyl) iridium(III) and derivatives thereof. Such complexes are also known with polypodal ligands, as for example described in US 7,332,232, WO 2016 / 124304 and WO 2019 / 158453. Even though these complexes with polypodal ligands show advantages over complexes that otherwise have the same ligand structure, whose individual ligands are not polypodally bridged, there is also still need for improvement, for example in terms of efficiency, voltage and lifetime.

[0003] It is therefore an object of the present invention to provide improved iridium complexes which are suitable as emitters for use in OLEDs. In particular, it is the object of the present invention to provide green and yellow emitting iridium complexes which have a particularly narrow emission spectrum and are therefore particularly suitable as emitters in top emission OLEDs.SUMMARY OF THE INVENTION

[0004] The present invention relates to compounds of formula (1)         Ir(L)     Formula (1) wherein the ligand L has a structure of formula (2): wherein the ligand L coordinates to the iridium atom via the positions marked with * and wherein the hydrogen atoms not explicitly shown may also be partially or completely replaced by deuterium, and wherein the symbols and indices used apply: Rat each occurrence is the same or different and is F or CN; Aris a phenyl or biphenyl group which may be unsubstituted or substituted by one or more radicals, each of which are the same or different and are selected from the group consisting of F, CN, Si(CH 3 ) 3 , a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms or a cyclic alkyl group having 4 to 8 C atoms; in this case the phenyl or biphenyl group or the substituents on this phenyl or biphenyl group are optionally partially or completely deuterated; R 1< at each occurrence is the same or different and is F, CN, a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms, a cyclic alkyl group having 4 to 8 C atoms, phenyl or biphenyl, wherein R 1< is optionally partially or completely deuterated; and wherein when two adjacent radicals R 1< represent a straight-chain, branched or cyclic alkyl group, the two radicals R 1< may form a ring system with one another; R 2< , R 3< at each occurrence is the same or different and is F, a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms or a cyclic alkyl group having 4 to 8 C atoms, wherein R 2< and R 3< are optionally partially or completely deuterated; and wherein two adjacent radicals R 2< or two adjacent radicals R 3< may form a ring system with one another; R 4< at each occurrence is the same or different and is a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms, a cyclic alkyl group having 4 to 8 C atoms, phenyl or biphenyl, wherein R 4< is optionally partially or completely deuterated; wherein when two adjacent radicals R 4< represent a straight-chain, branched or cyclic alkyl group, the two radicals R 4< may form a ring system with one another; R 5< at each occurrence is the same or different and is a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms or a cyclic alkyl group having 4 to 8 C atoms; wherein R 5< is optionally partially or fully deuterated; wherein two adjacent radicals R 5< may form a ring system with one another; R 6< , R 7< at each occurrence is the same or different and is H, D, CH 3 or C 2 H 5 , wherein the CH 3 group or the C 2 H 5 group is optionally partially or completely deuterated; ris 1 or 2; sis 0 or 1; mat each occurrence is the same or different and is 0, 1, 2, 3 or 4; n, oat each occurrence of is the same or different and is 0, 1, 2, or 3; pis 0, 1 or 2; qis 0, 1, 2, or 3; with the proviso that the sum of q + r + s ≤ 4. BRIEF DESCRIPTION OF THE DRAWINGS

[0005] Figure 1 shows the photoluminescence spectrum (ca. 10 -5< M in degassed toluene) of compound Ir3 according to the invention and the reference emitters Ref-D1, Ref-D2 and Ref-D3. Figure 2 shows the photoluminescence spectra (ca. 10 -5< M in degassed toluene) of compounds Ir3, Ir178, Ir179 according to the invention and the reference emitter Ref-D3. DETAILED DESCRIPTION

[0006] Surprisingly, it was found that iridium complexes with a hexadentate tripodal ligand having the structure described below solve this problem and are very well suited for use in an organic electroluminescence device . These iridium complexes and organic electroluminescence devices containing these complexes are therefore the subject of the present invention.

[0007] Thus, the subject-matter of the invention is a compound of formula (1),         Ir(L)     Formula (1) wherein the ligand L has a structure represented by the following formula (2): wherein the ligand L coordinates to the iridium atom via the positions marked with * and wherein the hydrogen atoms not explicitly shown may also be partially or completely replaced by deuterium, and wherein the symbols and indices used apply: Rat each occurrence is the same or different and is F or CN; Aris a phenyl or biphenyl group which may be unsubstituted or substituted by one or more radicals each of which are the same or different and are selected from the group consisting of F, CN, Si(CH 3 ) 3 , a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms or a cyclic alkyl group having 4 to 8 C atoms; the phenyl or biphenyl group or the substituents on this phenyl or biphenyl group are optionally partially or completely deuterated; R 1< at each occurrence is the same or different and is F, CN, a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms, a cyclic alkyl group having 4 to 8 C atoms, phenyl or biphenyl, wherein R 1< is optionally partially or completely deuterated; and wherein when two adjacent radicals R 1< represent a straight-chain, branched or cyclic alkyl group, the two radicals R 1< may form a ring system with one another; R 2< , R 3< at each occurrence is the same or different and is F, a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms or a cyclic alkyl group having 4 to 8 C atoms; wherein R 2< and R 3< are optionally partially or completely deuterated; and wherein two adjacent radicals R 2< or two adjacent radicals R 3< may form a ring system with one another; R 4< at each occurrence is the same or different and is a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms, a cyclic alkyl group having 4 to 8 C atoms, phenyl or biphenyl; wherein R 4< is optionally partially or completely deuterated; wherein when two adjacent radicals R 4< represent a straight-chain, branched or cyclic alkyl group, the two radicals R 4< may form a ring system with one another; R 5< at each occurrence is the same or different and is a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms or a cyclic alkyl group having 4 to 8 C atoms; wherein R 5< is optionally partially or completely deuterated; wherein two adjacent radicals R 5< may form a ring system with one another; R 6< , R 7< at each occurrence of is the same or different and is H, D, CH 3 or C 2 H 5 , wherein the CH 3 group or the C 2 H 5 group is optionally partially or completely deuterated; ris 1 or 2; sis 0 or 1; mat each occurrence is the same or different and is 0, 1, 2, 3 or 4; n, oat each occurrence is the same or different and is 0, 1, 2, or 3; pis 0, 1 or 2; qis 0, 1, 2, or 3; with the proviso that the sum of q + r + s ≤ 4.

[0008] The ligand L of formula (2) is thus a hexadentate, tripodal ligand with two bidentate phenylpyridine partial ligands and one bidentate dibenzofuranyl-pyridine partial ligand. The complex Ir(L) of formula (1) formed with this ligand thus has the following structure: wherein the symbols and indices have the meanings given above and the hydrogen atoms not shown may also be partially or completely replaced by deuterium.

[0009] In this case, the coordinating dibenzofuran group has, as a mandatory feature on the non-coordinating phenyl ring, at least one group R representing fluorine and / or cyano.

[0010] If two radicals R 1< or two radicals R 2< or two radicals R 3< or two radicals R 4< or two radicals R 5< form a ring system with one another, this can be monocyclic or polycyclic. In this case, the radicals that form a ring system with one other are adjacent, i.e., these radicals bond to carbon atoms that are directly bonded to one another. By the formulation that two radicals can form a ring with each other, it is to be understood in the context of the present description that the two radicals are linked to each other by a chemical bond with formal cleavage of two hydrogen atoms. This is illustrated by the following scheme:

[0011] In a preferred embodiment of the invention, the radicals R 1< or R 2< or R 3< or R 4< or R 5< do not form a ring system with each other.

[0012] A cyclic alkyl group within the meaning of the present invention is understood to be a monocyclic, a bicyclic or a polycyclic group .

[0013] In the context of the present invention, a C 1 - to C 10 -alkyl group includes, for example, the radicals methyl, ethyl, n-propyl, i-Propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neo-pentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methyl cyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2,2,2]octyl, 2-bicyclo[2,2,2]octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, Adamantyl, 1,1-dimethyl-n-hex-1-yl, 1,1-dimethyl-n-hept-1-yl, 1,1-dimethyl-n-oct-1-yl, 1,1-diethyl-n-hex-1-yl, 1-(n-propyl)-cyclohex-1-yl and 1-(n-butyl)-cyclohex-1-yl. These can also each be partially or fully permanently deuterated.

[0014] If the indices m, n, o, p, q or s = 0, a hydrogen atom or a deuterium atom is bonded instead of the substituents.

[0015] In a preferred embodiment of the invention, r = 1, and the ligand has a structure of the following formula (3), (4), (5), or (6), wherein the symbols and indices used have the meanings given above and the hydrogen atoms which are not explicitly shown may also be partially or completely replaced by deuterium. In this context, each occurrence of R 6< is preferably the same or different and represents H, D or CH 3 , which may also be partially or completely deuterated, and each occurrence of R 7< is preferably the same or different and represents H or D. In this context, the ligand of the formula (4) is preferred .

[0016] When r = 2, it is preferred that one residue R represents CN, and the other residue R represents F.

[0017] It is preferred that when R = CN, s = 0, i.e., the ligand does not have a group Ar. Further, it is preferred when R = F that s = 1, i.e., that the ligand has a group Ar. Furthermore, it is preferred when R = F that s = 0 and q = 1, wherein R 5< represents a cyclopentyl or cyclohexyl group, which is optionally partially or fully deuterated.

[0018] When s = 1, the ligand preferably has a structure according to one of the following formulae (7), (8), (9) or (10), wherein the symbols and indices used have the meanings given above and the hydrogen atoms which are not explicitly shown may also be partially or completely replaced by deuterium. In these formulae, R preferably represents F. Each occurrence of R 6< is preferably the same or different and represents H, D or CH 3 , which may also be partially or completely deuterated, and each occurrence of R 7< is preferably the same or different and represents H or D. Preferred is the ligand of the formula (7).

[0019] In a particularly preferred embodiment, r = 1, R = CN and s = 0 and the ligand L represents a structure of the following formula (11a), or r = 1, R = F and s = 1 and the ligand L represents a structure of the following formula (11b), or r = 1, R = F or CN, s = 0 and q = 1 and the ligand L represents a structure of the following formula (11c), wherein the symbols and indices used have the meanings given above, the hydrogen atoms which are not explicitly shown may also be partially or completely replaced by deuterium, R 6< is H, D, CH 3 or CD 3 and R 5< in formula (11c) preferably represents a cyclopentyl or cyclohexyl group which is optionally partially or completely deuterated, deuteration at the C atom with which this group bonds to the dibenzofuran, i.e. at the tertiary C atom, being particularly preferred.

[0020] In another preferred embodiment of the present invention, a deuterium is bound in all ortho-positions to R in which Ar or R 5< is not bound. Preferred embodiments of formulae (11a), (11b) and (11c) for q = 0 are thus the following formulae (11a-1), (11b-1) and (11c-1), respectively, wherein the symbols and indices used have the abovementioned meanings, the hydrogen atoms which are not explicitly shown may also be partially or completely replaced by deuterium, each occurrence of R 6< is identical or different and is H, D, CH 3 or CDs, and R 5< in formula (11c-1) is preferably a cyclopentyl or cyclohexyl group which is optionally partially or completely deuterated, where in particular deuteration at the C atom with which this group bonds to the dibenzofuran is preferred.

[0021] Preferred embodiments of the bridgehead, i.e., the triethylenebenzene group, are the following structures (A) to (I): wherein the dashed bond represents the bond to the two phenylpyridine partial ligands and to the dibenzofuranpyridine partial ligand, respectively. Here, H / D in formulas (D) to (I) is the same or different for hydrogen or deuterium, and the methyl groups and / or the benzene group in these formulas may be partially or fully deuterated. In formulae (G), (H) and (I), the ethylene group which is not substituted by methyl groups is attached to the pyridine-dibenzofuran partial ligand, and the two ethylene groups, each substituted by two or four methyl groups, are attached to the two phenylpyridine partial ligands. Preferred embodiments are the groups of formula (B), (E) and (H).

[0022] Preferred embodiments of substituents Ar and R 1< to R 7< are elaborated below.

[0023] Ar is preferably a phenyl group which is optionally partially or fully deuterated and which is otherwise unsubstituted or substituted by a methyl group which is optionally partially or fully deuterated.

[0024] Particularly preferred groups Ar are selected from the groups of the following formulae (Ar-1) to (Ar-4), wherein the dashed bond represents binding to the dibenzofuran group of the ligand.

[0025] In another preferred embodiment of the invention, each occurrence of R 1< is the same or different and is selected from the group consisting of CN, a straight chain alkyl group having 1 to 4 C atoms, a branched alkyl group having 3 to 5 C atoms, a cyclic alkyl group having 5 or 6 C atoms, or a phenyl group, each of which groups are optionally partially or fully deuterated. In a particularly preferred embodiment of the invention, each occurrence of R 1< is the same or different and is selected from the group consisting of methyl, iso-propyl, tert-butyl, neo-pentyl, phenyl, cyclopentyl or cyclohexyl, wherein these groups in each case are optionally partially or completely deuterated. It is particularly preferred if the benzylic positions, i.e., the positions that bind directly to the phenyl ring, are deuterated.

[0026] In this case, each occurrence of the index m is preferably the same or different and is 0, 1, 2 or 3, particularly preferably 0, 1 or 2 and most preferably 0 or 1.

[0027] In a further embodiment of the invention, each occurrence of R 2< and R 3< is the same or different and is selected from the group consisting of a straight-chain alkyl group having 1 to 4 C atoms, a branched alkyl group having 3 to 5 C atoms, or a cyclic alkyl group having 5 or 6 C atoms, each of which groups are optionally partially or fully deuterated. In a particularly preferred embodiment of the invention, each occurrence of R 2< and R 3< is the same or different and is selected from the group consisting of methyl, iso-propyl, tert-butyl, neo-pentyl, cyclopentyl or cyclohexyl, wherein these groups are optionally partially or completely deuterated. It is particularly preferred if the benzylic positions, i.e., the positions that bind directly to the pyridine ring, are deuterated.

[0028] Thereby each occurrence of the indices n and o is preferably the same or different and is 0, 1 or 2, especially preferably 0 or 1.

[0029] In another preferred embodiment of the invention, each occurrence of R 4< is the same or different selected from the group consisting of a straight chain alkyl group having 1 to 4 C atoms, a branched alkyl group having 3 to 5 C atoms, a cyclic alkyl group having 5 or 6 C atoms, or phenyl, each of which groups are optionally partially or fully deuterated. In a particularly preferred embodiment of the invention, each occurrence of R 4< is the same or different and is selected from the group consisting of methyl, iso-propyl, tert-butyl, neo-pentyl or phenyl, wherein these groups are optionally partially or completely deuterated. It is particularly preferred if the benzylic positions, i.e., the positions that bind directly to the dibenzofuran, are deuterated.

[0030] In another preferred embodiment of the invention, each occurrence of R 5< is the same or different and is selected from the group consisting of a straight chain alkyl group having 1 to 4 C atoms, a branched alkyl group having 3 to 5 C atoms, or a cyclic alkyl group having 5 or 6 C atoms, which groups are optionally partially or fully deuterated. In a particularly preferred embodiment of the invention, each occurrence of R 5< is the same or different and is selected from the group consisting of methyl, iso-propyl, tert-butyl, neo-pentyl, cyclopentyl or cyclohexyl, wherein these groups may optionally be partially or completely deuterated. It is particularly preferred if the benzylic positions, i.e., the positions that bind directly to the dibenzofuran, are deuterated.

[0031] In another preferred embodiment of the invention, each occurrence of R 6< is the same or different and is H, D, CH 3 or CDs .

[0032] In another preferred embodiment of the invention, each occurrence of R 7< is the same or different and is H or D, in particular D.

[0033] The index p is preferably 0 or 1 and particularly preferably 0. The index q is preferably 0 or 1 and particularly preferably 0.

[0034] In another preferred embodiment of the invention, the two phenylpyridine partial ligands are identical, i.e. the substituents R 1< on the two partial ligands are the same, the substituents R 2< on the two partial ligands are the same, the indices m are the same and the indices n are the same, and when substituents R 1< and / or R 2< are present, they are each attached to the two phenylpyridine partial ligands at the same position.

[0035] Furthermore, it is preferred if the above-mentioned preferred embodiments occur simultaneously. Thus, ligands of the formulae (2) to (11), (11a), (11b), (11c), (11a-1), (11b-1) and (11c-1), for which applies, are preferred: Aris a phenyl group which is optionally partially or fully deuterated and which is optionally substituted by a methyl group which is partially or fully deuterated; R 1< at each occurrence is the same or different and is selected from the group consisting of CN, a straight chain alkyl group having 1 to 4 C atoms, a branched alkyl group having 3 to 5 C atoms, a cyclic alkyl group having 5 or 6 C atoms, or a phenyl group, each of which groups are optionally partially or fully deuterated; R 2< , R 3< at each occurrence is the same or different and is selected from the group consisting of a straight chain alkyl group having 1 to 4 C atoms, a branched alkyl group having 3 to 5 C atoms, or a cyclic alkyl group having 5 or 6 C atoms, each of which groups are optionally partially or fully deuterated; R 4< at each occurrence is the same or different and is selected from the group consisting of a straight chain alkyl group having 1 to 4 C atoms, a branched alkyl group having 3 to 5 C atoms, a cyclic alkyl group having 5 or 6 C atoms, or phenyl, each of which groups are optionally partially or fully deuterated; R 5< at each occurrence is the same or different and is selected from the group consisting of a straight chain alkyl group having 1 to 4 C atoms, a branched alkyl group having 3 to 5 C atoms, or a cyclic alkyl group having 5 or 6 C atoms, each of which groups are optionally partially or fully deuterated; R 6< at each occurrence is the same or different and is H, D, or CH 3 , which are optionally partially or completely deuterated; R 7< at each occurrence is the same or different and is H or D; mat each occurrence is the same or different and is 0, 1, 2 or 3; n, oat each occurrence is the same or different and is 0, 1 or 2; pis 0 or 1; qis 0 or 1; sis 0 for R = CN and is 1 for R = F.

[0036] Particularly preferred are ligands of the formulae (2) to (11), (11a), (11b), (11c), (11a-1), (11b-1) and (11c-1), for which holds: Aris selected from the groups of the following formulas (Ar-1) to (Ar-4), as described above; R 1< at each occurrence is the same or different and is selected from the group consisting of methyl, iso-propyl, tert-butyl, neo-pentyl, cyclopentyl, cyclohexyl or phenyl, each of which groups are optionally partially or fully deuterated; R 2< , R 3< at each occurrence is the same or different and is selected from the group consisting of methyl, iso-propyl, tert-butyl, neo-pentyl, cyclopentyl or cyclohexyl, each of which groups are optionally partially or fully deuterated; R 4< at each occurrence is the same or different and is selected from the group consisting of a straight chain alkyl group having 1 to 4 C atoms, a branched alkyl group having 3 to 5 C atoms, a cyclic alkyl group having 5 or 6 C atoms, or phenyl, each of which groups are optionally partially or fully deuterated; R 5< at each occurrence is the same or different and is selected from the group consisting of a straight chain alkyl group having 1 to 4 C atoms, a branched alkyl group having 3 to 5 C atoms, or a cyclic alkyl group having 5 or 6 C atoms, each of which groups are optionally partially or fully deuterated; R 6< at each occurrence is the same or different and is H, D, CH 3 or CDs ; R 7< at each occurrence is the same or different and is H or D; mat each occurrence is the same or different and is 0, 1 or 2, more preferably 0 or 1; n, oat each occurrence is the same or different and is 0 or 1; p, qis 0; sis 0 for R = CN and is 1 for R = F.

[0037] The above-mentioned preferred embodiments can be combined with each other as desired. In a particularly preferred embodiment of the invention, the above preferred embodiments apply simultaneously.

[0038] Examples of suitable structures according to the invention are the compounds illustrated below. 12 34 56 78 910 1112 1314 1516 1718 1920 2122 2324 2526 2728 2930 3132 3334 3536 3738 3940 4142 4344 4546 4748 4950 5152 5354 5556 5758 5960 6162 6364 6566 6768 6970 7172 7374 7576 7778 7980 8182 8384 8586 8788 8990 9192 9394 9596 9798 99100 101103 103104 105106 107108 109110 111112 113114 115116 117118 119120 121122 123124 125126 127128 129130 131132 133134 135136 137138 139140 141142 143144 145146 147148 149150 151152 153154 155156 157158 159160 161162 163164 165166 167168 169170 171172 173174 175176 177178 179180 181182 183184 185186 187188 189190 191192 193194

[0039] The metal complexes according to the invention are chiral structures. If, in addition, the ligand L is also chiral, the formation of diastereomers and several pairs of enantiomers is possible. The complexes according to the invention then include both the mixtures of the diastereomers and the corresponding racemates, as well as the individual isolated diastereomers and enantiomers.

[0040] If ligands with two identical partial ligands are used in ortho-metalation, a racemic mixture of the C 1 -symmetric complexes, i.e., the Δ and the A enantiomers, is usually obtained. These can be separated by common methods (chromatography on chiral materials / columns or racemate separation by crystallization) as shown in the following scheme, wherein for clarity the optional substituents are not shown:

[0041] Racemate separation via fractional crystallization of diastereomeric salt pairs can be performed according to standard methods. For this purpose, it is useful to oxidize the neutral Ir(III) complexes (e.g., with peroxides, H 2 O 2 or electrochemically), to add the salt of an enantiomerically pure, monoanionic base (chiral base) to the cationic Ir(IV) complexes thus produced, to separate the diastereomeric salts thus produced by fractionized crystallization, and then to convert them to the enantiomeric salts with the aid of a reduction agent (e.g., zinc, hydrazine hydrate, ascorbic acid, etc.). e.g., zinc, hydrazine hydrate, ascorbic acid, etc.) to the enantiomerically pure neutral complex, as shown schematically below:

[0042] In addition, enantiomerically pure or enantiomerically enriched synthesis is possible by complexation in a chiral medium (e.g., R- or S-1,1-binaphthol).

[0043] If ligands with three different part ligands are used in the complexation, a diastereomeric mixture of the complexes is usually obtained, which can be separated by common methods (chromatography, crystallization, etc.).

[0044] Enantiomerically pure C 1 -symmetric complexes can also be specifically synthesized. For this purpose, an enantiomerically pure C 1 -symmetric ligand is presented, complexed, the diastereomeric mixture obtained is separated and then the chiral group is cleaved off.

[0045] The synthesis of the ligands can be presented starting from the boron esters (1) and (3) known from the literature. For the sake of clarity, the following description of the synthesis deliberately omits substituents at the bridgehead, at the phenyl or pyridine rings and, apart from the substituent R, also at the dibenzofuran.

[0046] The boronic ester (1) is regioselectively coupled to the 2-position of a 2,6-dihalopyridine in a Suzuki coupling to form the 5-halopyridine-2-dibenzofuran (2) (Scheme 1).

[0047] The boronic ester (3) can first be converted to the bromide (4) by reaction with copper(II) bromide (Scheme 2, Step 2), which can then be converted to the alkyne (5) by Sonogashira reaction with trimethylsilylacetylene (Scheme 2, Step 3).

[0048] The alkyne (5) can be deprotected in situ by reaction with methanol in the presence of potassium carbonate and then coupled with the 5-halopyridine-2-dibenzofuran (2) to give the alkyne (6) (Scheme 3, step 4), which can then be Pd-catalyzed with hydrogen to give the ligand (7) (Scheme 3, step 5). Subsequent ortho-metallation of the ligand is possible according to procedures known in the literature. For example, the reaction starting from iridium tris-acetylacetonate or tris(2,2,6,6-tetramethyl-3,5-heptane dionato-κO 3< ,κO 5< )-iridium in a hydroquinone melt at elevated temperature, for example, in the range of about 250 °C, (WO 2016 / 124304) or from going from iridium(III)acetate in a salicylic acid-mesitylene mixture at elevated temperature, for example in the range of about 160 °C, (WO 2021 / 013775), the complexes according to the invention in good yields (Scheme 3, step 6). These are finally purified by methods known from literature (chromatography, hot extraction crystallization, fractional sublimation).

[0049] If deuterated synthesis building blocks (1) or (3) are used, or if hydrogenation of the alkyne (6) is carried out with deuterium (D 2 ) instead of hydrogen (H 2 ), partially or fully deuterated complexes (8) can be obtained. Furthermore, non-deuterated or partially deuterated complexes can be further deuterated at the alkyl and aryl groups by methods known from literature (WO 2019 / 158453).

[0050] The synthesis of the compounds according to the invention is possible in principle by reacting an iridium salt with the corresponding free ligand.

[0051] Therefore, a further object of the present invention is a process for preparing the compounds of the invention by reacting the corresponding free ligands with iridium alkoxides of formula (Ir-1), with iridium ketoketonates of formula (Ir-2), with iridium halides of formula (Ir-3) or with iridium carboxylates of formula (Ir-4), wherein R has the meanings given above, Hal = F, Cl, Br or I and the iridium educts may also be present as the corresponding hydrates. In this context, alkyl preferably stands for an alkyl group having 1 to 4 C atoms.

[0052] Iridium compounds bearing both alkoxide and / or halide and / or hydroxide as well as ketoketonate residues can also be used . These compounds may also be charged. Corresponding iridium compounds that are particularly suitable as reactants are disclosed in WO 2004 / 085449. Particularly suitable are [IrCl 2 (acac) 2 ] -< , for example Na[IrCl 2 (acac) 2 ], metal complexes with acetylacetonate derivatives as ligand, for example Ir(acac) 3 or tris(2,2,6,6-tetramethylheptane-3,5-dionato)iridium, and IrCl 3 ·xH 2 O, where x usually stands for a number between 2 and 4.

[0053] The synthesis of the complexes is preferably carried out as described in WO 2002 / 060910 and in WO 2004 / 085449. Synthesis in an organic acid or a mixture of an organic acid and an organic solvent, as described in WO 2021 / 013775, is also particularly suitable, with particularly suitable reaction media being, for example, acetic acid or a mixture of salicylic acid and an organic solvent, for example mesitylene. In this context, the synthesis can also be activated thermally, photochemically and / or by microwave radiation. Furthermore, the synthesis can also be carried out in the autoclave at elevated pressure and / or temperature by .

[0054] The reactions can be carried out without the addition of solvents or melting aids in a melt of the corresponding ligands to be o metalated. If necessary, solvents or melting aids can also be added. Suitable solvents are protic or aprotic solvents, such as aliphatic and / or aromatic alcohols (methanol, ethanol, iso-propanol, t-butanol, etc.), oligo- and polyalcohol's (ethylene glycol, 1,2-propanediol, glycerol, etc.), alcohol ethers (ethoxyethanol, diethylene glycol, triethylene glycol, polyethylene glycol, etc.), ethers (di- and triethylene glycol dimethyl ether, diphenyl ether, etc.), aromatic, heteroaromatic and or aliphatic hydrocarbons (toluene, xylene, mesitylene, chlorobenzene, pyridine, lutidine, quinoline, isoquinoline, tridecane, hexadecane, etc.), amides (DMF, DMAC, etc.), lactams (NMP), sulfoxides (DMSO), or sulfones (dimethyl sulfone, sulfane, etc.). Suitable melting aids are compounds that are solid at room temperature but melt and dissolve the reactants when the reaction mixture is heated, resulting in a homogeneous melt. Particularly suitable are biphenyl, m-terphenyl-, triphenylene, R- or S-binaphthol or also the corresponding racemate, 1,2-, 1,3-, 1,4-bis phenoxybenzene, tri phenyl phosphine oxide, 18-crown-6, phenol, 1-naphthol, hydroquinone, etc. The use of hydroquinone is particularly preferred.

[0055] As described above and in the example section, the synthesis of the fully or partially deuterated complexes is possible either by using the partially or fully deuterated ligand in the complexation reaction and / or by deuterating the complex after the complexation reaction.

[0056] By these methods, optionally followed by purification, such as recrystallization or sublimation, the compounds of the invention according to formula (1) can be obtained in high purity, preferably more than 99% (determined by 1< H-NMR and / or HPLC).

[0057] Formulations of the iridium complexes of the invention are required for processing the iridium complexes of the invention from liquid phase, for example by spin coating or by pressure processes. These formulations may be, for example, solutions, dispersions or emulsions. It may be preferred to use mixtures of two or more solvents for this purpose. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methylbenzoate, mesitylene, tetralin, veratrol, THF, methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-)-fenchone, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methyl naphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethyl anisole, acetophenone, α-terpineol Benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, NMP, p-cymene, phenetol, 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, di ethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetra ethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexyl benzene, heptylbenzene, octylbenzene, 1,1-Bis(3,4-dimethylphenyl)ethane, hexamethylindane, 2-methylbiphenyl, 3-Methylbiphenyl, 1-Methylnaphthalene, 1-ethylnaphthalene, ethyl octanoate, sebacic acid diethyl ester, octyl octanoate, heptylbenzene, menthyl isovalerate, cyclohexyl hexanoate or mixtures of these solvents.

[0058] A further object of the present invention is therefore a formulation comprising at least one compound according to the invention and at least one further compound. The further compound may be, for example, a solvent, in particular one of the solvents mentioned above or a mixture of these solvents. However, the further compound may also be a further organic or inorganic compound which is also used in the electronic device, for example a matrix material. This further compound may also be polymeric.

[0059] The compound according to the invention can be used in an electronic device as an active component, preferably as an emitter in the emissive layer of an organic electroluminescent device. A further object of the present invention is thus the use of the compounds according to the invention in an electronic device, in particular in an organic electroluminescence device.

[0060] Still another object of the present invention is an electronic device containing at least one compound according to the invention, in particular an organic electroluminescent device.

[0061] An electronic device is understood to be a device which contains an anode, a cathode and at least one layer, this layer containing at least one organic or organometallic compound. The electronic device according to the invention thus contains an anode, cathode and at least one layer, which contains at least one iridium complex according to the invention. In this context, preferred electronic devices are selected from the group consisting of organic electroluminescence devices (OLEDs, PLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs)-, where this includes both purely organic solar cells and dye-sensitized solar cells, organic optical detectors, organic photoreceptors, organic field quench devices (O-FQDs), light-emitting electrochemical cells (LECs), oxygen sensors or organic laser diodes (O-Lasers), containing in at least one layer at least one compound of the invention. Compounds that emit in the infrared are suitable for use in organic infrared electroluminescent devices and infrared sensors. Organic electroluminescence devices are particularly preferred. Active components are generally the organic or inorganic materials which are introduced between the anode and cathode, for example charge injection, charge transport or charge blocking materials, but in particular emission materials and matrix materials. The compounds according to the invention show particularly good properties as emission materials in organic electroluminescence devices. A preferred embodiment of the invention is therefore organic electroluminescent devices . Furthermore, the compounds according to the invention can be used for the generation of singlet oxygen or in photocatalysis.

[0062] The organic electroluminescent device includes cathode, anode and at least one emitting layer. In addition to these layers, it may contain other layers, for example one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking layers, electron blocking layers, charge generation layers and / or organic or inorganic p / n transitions. It is possible that one or more hole transport layers are p-doped and / or that one or more electron transport layers are n-doped. Likewise, interlayers can be introduced between two emitting layers, which, for example, exhibit an exciton-blocking function and / or control the charge balance in the electroluminescence before direction and / or generate charges (charge-generation layer, e.g., in layer systems with multiple emitting layers, e.g., in white-emitting OLED devices). It should be noted, however, that not necessarily each of these layers must be present.

[0063] The organic electroluminescence device may contain one emitting layer, or it may contain several emitting layers. If several emitting layers are present, these preferably have in total several emission maxima between 380 nm and 750 nm, so that overall white emission results, i.e., different emitting compounds that can fluoresce or phosphoresce are used in the emitting layers. Particularly preferred are three-layer systems, wherein the three layers show blue, green and orange or red emission, or systems which have more than three emitting layers. It can also be a hybrid system, where one or more layers fluoresce, and one or more other layers phosphoresce. Tandem OLEDs are a preferred embodiment. White emitting organic electroluminescence can be used for lighting applications or with color filters also for full color displays.

[0064] In a preferred embodiment of the invention, the organic electroluminescent device contains the compound of the invention as an emitting compound in one or more emitting layers, in particular in a green emitting layer.

[0065] When the compound according to the invention is used as an emitting compound in an emitting layer, it is preferably used in combination with one or more matrix materials. The mixture of the compound according to the invention and the matrix material contains between 0.1 and 99 vol%, preferably between 1 and 90 vol%, particularly preferably between 3 and 40 vol%, especially between 5 and 15 vol% of the compound according to the invention relative to the total mixture of emitter and matrix material. Accordingly, the mixture contains between 99.9 and 1% by volume, preferably between 99 and 10% by volume, particularly preferably between 97 and 60% by volume, especially between 95 and 85% by volume of the matrix material based on the total mixture of emitter and matrix material.

[0066] In general, all materials known in the prior art can be used as matrix material. Preferably, the triplet level of the matrix material is higher than the triplet level of the emitter.

[0067] Suitable matrix materials for the compounds according to the invention are ketones, phosphine oxides, sulfoxides and sulfones, e.g. according to WO 2004 / 013080, WO 2004 / 093207, WO 2006 / 005627 or WO 2010 / 006680, triarylamines, carbazole derivatives, e.g. CBP (N,N-biscarbazolylbiphenyl), 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, biscarbazole derivatives, indolocarbazole derivatives, e.g. according to WO 2007 / 063754 or WO 2008 / 056746, indenocarbazole derivatives, e.g. according to WO 2010 / 136109 or WO 2011 / 000455, azacarbazoles, e.g. according to EP 1617710, EP 1617711, EP 1731584, JP 2005 / 347160, bipolar matrix materials, e.g. according to WO 2007 / 137725, silanes, e.g. according to WO 2005 / 111172, azaboroles or boronic esters, e.g. according to WO 2006 / 117052, diazasilol derivatives, e.g. according to WO 2010 / 054729, diazaphosphol derivatives, e.g. according to WO 2010 / 054730, triazine derivatives, e.g. according to WO 2010 / 015306, WO 2007 / 063754 or WO 2008 / 056746, zinc complexes, e.g. according to EP 652273 or WO 2009 / 062578, dibenzofuran derivatives, e.g. according to WO 2009 / 148015 or WO 2015 / 169412, or bridged carbazole derivatives, e.g. according to US 2009 / 0136779, WO 2010 / 050778, WO 2011 / 042107 or WO 2011 / 088877. For solution-processed OLEDs, polymers, e.g., according to WO 2012 / 008550 or WO 2012 / 048778, oligomers or dendrimers, e.g., according to Journal of Luminescence 183 (2017), 150-158, are also suitable as matrix materials.

[0068] It may also be preferred to use several different matrix materials as a mixture, in particular at least one electron-conducting matrix material and at least one hole-conducting matrix material. For example, a preferred combination is the use of an aromatic ketone, a triazine derivative, a pyrimidine derivative, a phosphine oxide derivative or an aromatic lactam with a triarylamine derivative or a carbazole derivative as a mixed matrix for the compound according to the invention. Equally preferred is the use of a mixture of a charge transporting matrix material and an electrically inert matrix material (so-called "wide bandgap host"), which is not or not substantially involved in the charge transport, as described, for example, in WO 2010 / 108579 or WO 2016 / 184540. Equally preferred is the use of two electron transporting matrix materials, for example triazine derivatives and lactam derivatives, as described, for example, in WO 2014 / 094964.

[0069] Examples of compounds suitable as matrix materials for the compounds of the invention are shown below.

[0070] Preferred biscarbazoles that can be used as matrix materials for the compounds according to the invention are the structures of the following formulae (12) and (13), wherein the following applies to the symbols used: Ar 1< at each occurrence is the same or different and is an aromatic or ring system having 5 to 40 aromatic ring atoms, preferably having 6 to 30 aromatic ring atoms, particularly preferably having 6 to 24 aromatic ring atoms, each of which may be substituted with one or more radicals R', preferably non-aromatic radicals R'; A'is NAr 1< , C(R') 2 , O or S, preferably C(R') 2 ; R'at each occurrence is the same or different and is H, D, F, CN, an alkyl group having 1 to 10 C atoms, preferably having 1 to 4 C atoms, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, preferably having 6 to 30 aromatic ring atoms, particularly preferably with 6 to 24 aromatic ring atoms, which may be substituted with one or more substituents selected from the group consisting of D, F, CN or an alkyl group with 1 to 10 C atoms, preferably with 1 to 4 C atoms.

[0071] Preferred embodiments of the compounds of formulae (12) or (13) are the compounds of the following formulae (12a) or (13a), respectively, wherein the symbols used have the above meanings.

[0072] Preferred dibenzofuran derivatives are the compounds of the following formula (14), wherein the oxygen can also be replaced by sulfur, so that a dibenzothiophene is formed, L 1< is a single bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, preferably having 6 to 24 aromatic ring atoms, which can also be substituted by one or more radicals R', but is preferably unsubstituted, and R' and Ar 1< have the meanings given above. In this context, the two groups Ar 1< , which bind to the same nitrogen atom, or a group Ar 1< and a group L, which bind to the same nitrogen atom, can also be linked to one another, for example to form a carbazole.

[0073] Preferred carbazolamines are the structures of the following formulae (15), (16) and (17), wherein L 1< , R' and Ar 1< have the above meanings.

[0074] Examples of suitable hole-conducting matrix materials are the compounds shown in the following table. H1H2H3 H4H5H6 H7H8H9 H10H11H12 H13H14H15 H16H17H18 H19H20H21 H22H23H24 H25H26H27 H28H29H30 H31H32H33 H34H35H36 H37H38H39 H40H41H42 H43H44H45 H46H47H48 H49H50H51 H52H53H54 H55H56H57

[0075] Preferred triazine or pyrimidine derivatives, which can be used as a mixture together with the compounds of the invention, are the compounds of the following formulae (18) and (19), wherein Ar 1< has the meanings given above.

[0076] Particularly preferred are the triazine derivatives of formula (18).

[0077] In a preferred embodiment of the invention, each occurrence of Ar 1< in formulas (18) and (19) is the same or different and is an aromatic or heteroaromatic ring system having 6 to 30 aromatic ring atoms, in particular having 6 to 24 aromatic ring atoms, which may be substituted by one or more radicals R'.

[0078] Examples of suitable electron-transporting compounds that can be used as matrix materials together with the compounds according to the invention are the compounds shown in the following table. E1E2E3 E4E5E6 E7E8E9 E10E11E12 E13E14E15 E16E17E18 E19E20E21 E22E23E24 E25E26E27 E28E29E30 E31E32E33 E34E35E36 E37E38E39 E40E41E42 E43E44E45 E46E47E48 E49E50E51 E52E53E54 E55E56E57 E58E59E60 E61E62E63 E64E65E66 E67E68E69 E70E71E72 E73E74E75 E76E77E78 E79E80E81 E81E82E83 E84E85E86 E87E88E89 E90E91E92 E93E94E95 E96E97E98 E99E100E101 E102E103E104 E105E106E107 E108E109E110 E111E112E113 E114E115E116 E117E118E119 E120E121E122 E123E124E125 E126E127E128 E129E130E131 E132E133E134 E135E136E137 E138E139E140 E141E142E143 E144E145E146 E147E148E149 E150E151E152 E153E154E155 E156E157E158 E159E160E161 E162E163E164 E165E166E167 E168E169E170 E171E172E173 E174E175E176 E177E178E179 E180E181E182 E183E184E185 E186E187E188 E189E190E191 E192E193E194 E195E196E197 E198E199E200 E201E202E203 E204E205E206 E207E208E209 E210E211E212 E213E214E215 E216E217E218 E219E220E221 E222E223E224 E225E226E227 E228E229E230 E231E232E233 E234E235E236 E237E238E239 E240E241E242 E243E244E245 E246E247E248 E249E250E251 E252E253E254 E255E256E257 E258E259E260 E261E262E263 E264E265E266 E267E268E269 E270E271E272 E273E274E275 E276E277E278 E279E280E281 E282E283E284 E285E286E287 E288E289E300 E301E302E303

[0079] In the further layers, generally all materials can be used as they are used for the layers according to the prior art, and the skilled person can combine any of these materials in an electronic device with the materials according to the invention without any inventive intervention.

[0080] Further preferred is an organic electroluminescent device, characterized in that one or more layers are coated by a sublimation process. In this process, the materials are vapor deposited in vacuum sublimation systems at an initial pressure of usually less than 10 -5< mbar, preferably less than 10 -6< mbar. It is also possible for the initial pressure to be even lower or even higher, for example less than 10 -7< mbar.

[0081] An organic electroluminescent device is also preferred, characterized in that one or more layers are coated using the OVPD (organic vapor phase deposition) process or with the aid of carrier gas sublimation. In this process, the materials are applied at a pressure between 10 -5< mbar and 1 bar. A special case of this process is the OVJP (Organic Vapour Jet Printing) process, in which the materials are applied directly through a nozzle and thus patterned (e.g., M. S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

[0082] Further preferred is an organic electroluminescent device, characterized in that one or more layers are produced from solution, such as by spin coating, or by any printing process, such as screen printing, flexographic printing, offset printing or nozzle printing, but especially preferably LITI (Light Induced Thermal Imaging, Thermo trans fer printing) or ink-jet printing. Soluble compounds are required for this, which can be obtained by suitable substitution, for example.

[0083] The organic electroluminescent device can also be fabricated as a hybrid system by depositing one or more layers of solution and vapor depositing one or more other layers. For example, it is possible to deposit an emitting layer containing a metal complex of the invention and a matrix material of solution and to vacuum evaporate a hole-blocking layer and / or an electron transport layer on top of it.

[0084] These methods are generally known to those skilled in the art and can be readily applied by them to organic electroluminescent devices containing compounds according to formula (1) or the preferred embodiments listed above.

[0085] The electronic devices according to the invention, in particular organic electroluminescent devices, have the unexpected advantage over the prior art of having a significantly narrower emission spectrum than corresponding complexes not bridged by a triethylenebenzene group. This is particularly an advantage for top emission devices, as it results in a higher current efficiency (in cd / A).

[0086] The invention is explained in more detail by the following examples without wishing to limit it. The person skilled in the art can manufacture further electrical devices in accordance with the invention from the shields without the intervention of the inventor and thus implement the invention in the entire field in question.EXPERIMENTAL EXAMPLES

[0087] The following syntheses are carried out under an inert gas atmosphere in dried solvents, unless otherwise specified. The metal complexes are additionally handled under exclusion of light or under yellow light. The solvents and reagents can be obtained, for example, from Sigma-ALDRICH and ABCR, respectively. The respective data in square brackets or the numbers given for individual compounds refer to the CAS numbers of the compounds known from literature. For compounds that can have several enantiomers, diastereomeric or tautomeric forms, one form is shown as a representative.Literature-known Synthons LS:

[0088] LS1 1673545-14-6LS2 2458817-56-4LS3 1638837-02-1LS4 2458817-52-0LS5 2714359-25-6LS6 2412928-17-5LS7 2229864-94-0LS8 2417213-49-9LS9 Synthesized as in US 2020 / 0251666 from 1349716-12-6LS100 2375158-15-7LS101 2375158-17-9LS102 2375158-19-1LS103 2375158-21-5LS104 Synthesized as in WO 2019 / 158453, Use of 1256833-52-9LS105 Synthesized as in WO 2019 / 158453, Use of 1381942-00-2LS106 Synthesized as in WO 2019 / 158453, Use of LS200LS200 Synthesized as in CN11227980A, Use of 72990-37-5 A) Synthesis of synthons S: Example S1:

[0089]

[0090] A mixture of 31.9 g (100 mmol) LS1, 14.8 g (100 mmol) 2,5- dichloropyridine [16110-09-1], 41.5 g (300 mmol) potassium carbonate, 702 mg (1 mmol) bis(triphenylphosphino)palladium dichloride [13965-03-2], 100 g glass spheres (3 mm diameter), 200 ml acetonitrile, and 200 ml methanol is heated for 16 h under weak reflux. Suction is applied while still warm over a Celite bed pre-slurried with acetonitrile, concentrate the filtrate to dryness, collect the residue in 400 ml dichloromethane (DCM) and 100 ml ethyl acetate (EA), and filter over a silica gel bed pre-slurried with DCM / EA (4:1). Add 200 ml methanol (MeOH) to the filtrate and slowly concentrate it in vacuo to about 100 ml, aspirate from the crystallized product, rewash twice with 30 ml MeOH each, and dry in vacuo. Yield: 22.6 g (74 mmol) 74 %; purity: ca. 98 % by 1< H NMR.

[0091] Similarly, the following compounds can be prepared in yields of about 70-90%: Ex.EductsProductS2LS2 16110-09-1S3LS2 886365-00-0S4LS2 1256833-52-9S5LS2 1381942-00-2S6LS2 1381933-49-8S7LS3 16110-09-1S8LS4 16110-09-1S9LS5 16110-09-1S10LS6 16110-09-1S11LS6 124420-75-3S12LS7 16110-09-1S13LS8 16110-09-1S14LS9 16110-09-1S15LS9 886365-00-0S16LS9 1256833-52-9S17LS9 1381942-00-2S18S2 Synthesized as in US 2020 / 0091442S19S10 Synthesized as in US 2020 / 0091442S20LS2 LS200S21LS6 LS200RefS1LS1 100124-06-9 Example S100: A) S100A

[0092]

[0093] A suspension of 56.7 g (100 mmol) LS100 in 500 ml MeOH is heated to 40 °C and then a solution of 46.9 g (210 mmol) copper(II) bromide in 400 ml water is added dropwise for 30 min with good stirring. After the addition is complete, heat for 12 h under reflux, then distill off about 500 ml and substitute with 500 ml of water. Allow to cool to room temperature with stirring, aspirate from the precipitated solid, wash three times with 200 ml water each time and aspirate dry. Suspend the solid in 600 ml DCM, add 200 ml conc. ammonia, stir for 2 h, separate the aqueous phase, wash the organic phase three times with 200 ml 2.5 N ammonia solution each, twice with 200 ml water each and once with brine and dry over magnesium sulfate. Aspirate from the desiccant, add 200 ml MeOH to the filtrate and concentrate to about 200 ml. Aspirate from the crystallized product, wash twice with a little methanol and dry in vacuo. Yield: 42.3 g (81 mmol) 81%; purity: about 97% by 1< H NMR.B) S100

[0094]

[0095] A mixture of 52.0 g (100 mmol) S100A, 28.6 ml (200 mmol) tri methyl silylacetylene [1066-54-2], 64.1 ml (500 mmol) triethylamine [121-44-8], 300 ml DMF, 572 mg (3 mmol) copper(I) iodide [7681-65-4], 2.11 g (3 mmol) bis(triphenylphosphino)palladium dichloride [13965-03-2] is stirred for 12 h at 75 °C. The reaction mixture is largely concentrated in vacuo, the residue is taken up in 500 ml DCM, washed three times each with 200 ml water and once with 200 ml total brine, and dried over magnesium sulfate. Filter off from the desiccant over a bed of Celite pre-slurried with DCM and concentrate the filtrate in vacuo. The crude product obtained is further reacted without further purification. Yield: 49.0 g (91 mmol) 91 %. Purity ca. 95 % by 1< H-NMR.

[0096] Similarly, the following compounds can be prepared in yields of about 70-90%: Ex.EductsProductS101LS101 S102LS102 S103LS103 S104LS104 S105LS105 S106LS106 S300S200 Example S200: a) Step 200a:

[0097]

[0098] A well-stirred mixture of 9.6 g (50 mmol) 1,1'-(5-methoxy-1,3-phenylene)bis-ethanone [35227-79-3], 23.4 g (100 mmol) 5-bromo-2-phenyl pyridine [27012-25-5], and 150 ml THF is mixed with 24.0 g (250 mmol) sodium tert-butanolate [865-48-5], 577 mg (1 mmol) XantPhos [161265-03-8], and 225 mg (1 mmol) palladium(II) acetate [3375-31-3], and then heated at reflux for 3 h. After cooling, the THF is removed in vacuo, the residue is taken up in 300 ml dichloromethane (DCM), the organic phase is washed twice with 150 ml water and once with 100 ml saturated brine, and dried over magnesium sulfate. Filter off the desiccant, remove the DCM in vacuo, and chromatograph (Torrent automatic column machine from Semrau) the residue. Yield: 15.6 g (31 mmol) 62 %; purity: ca. 97 % by 1< H-NMR.b) Step 200b:

[0099]

[0100] To a well-stirred solution of 18.3 g (50 mmol) 200a in 1000 ml tetrahydrofuran (THF), tempered to 25 °C, add dropwise for 5 min 100 ml (100 mmol) potassium hexamethyldisilazide (KHMDS) [40949-94-0], 1M in THF and stir for 15 min. Then add 3.4 ml (100 mmol) of methyl iodide [74-88-4] at a time and stir for 30 min. Then, 100 ml (100 mmol) of potassium hexamethyldisilazide (KHMDS), 1M in THF is added again to the reaction mixture during 5 min and stirring is continued for 15 min. Then add 3.4 ml (100 mmol) of methyl iodide at a time and stir for 30 min. Then, 10 ml (10 mmol) of potassium hexamethyldisilazaid KHMDS), 1M in THF is added to the reaction mixture again during 5 min and stirring is continued for 15 min. Then add 0.34 ml (10 mmol) of methyl iodide at a time and re-stir for 1 h. Remove the THF in vacuo, take up the residue in 300 ml dichloromethane (DCM), wash the organic phase twice with 150 ml water each and once with 100 ml saturated brine, and dry over magnesium sulfate. Filter off the desiccant, remove the DCM in vacuo, and chromatograph (Torrent automatic column machine from Semrau) the residue. Yield: 20.1 g (36 mmol) 72 %; purity: ca. 97 % by 1< H-NMR.c) Step 200c:

[0101]

[0102] To a well-stirred solution of 55.5 g (100 mmol) 200b in 1500 ml THF, cooled to 0 °C, add 15.2 g (400 mmol) lithium aluminum-hydride [16853-85-3] in portions and stir for 15 min. Allow the reaction mixture to warm to room temperature, stir for 1 h, cool again to 0 °C, then add dropwise 15 ml water (caution: exothermic reaction, gas evolution!), 15 ml 15 wt% aqueous NaOH, and 45 ml water, and stir for 30 min. Filter off the precipitated aluminum salts, concentrate the filtrate to dryness, collect the residue in 300 ml DCM and 100 ml ethyl acetate (EA), filter over a silica gel bed pre-slurried with DCM:EA (3:1 vv), and remove the solvent in vacuo. Yield: 52.9 g (95 mmol), 95% diastereomer mixture; purity: ca. 97% by 1< H NMR.d) Step 200d:

[0103]

[0104] To a solution of 55.8 g (100 mmol) 200c in 500 ml glacial acetic acid, add 263.4 ml aqueous hydriodic acid (57 wt%) and 49.3 ml aqueous hypophosphoric acid (50 wt%), then stir for 60 h. The solution is then mixed with a solution of 0.5 g (100 mmol) 200c in 500 ml glacial acetic acid. After cooling, pour onto 5 kg ice and then adjust to pH ~ 7 by adding solid NaOH in portions, extract the aqueous phase three times with 300 ml DCM, wash the combined organic phases two times with 200 ml water and once with 200 ml saturated brine, and then dry over magnesium sulfate. Filter off the desiccant and concentrate the filtrate to dryness. Yield: 47.7 g (93 mmol), 93 %; purity: about 97 % by 1< H-NMR.e) Step 200e:

[0105]

[0106] To a well-stirred mixture of 51.3 g (100 mmol) 200d, 10.5 ml (130 mmol) pyridine [110-86-1], and 300 ml DCM cooled to 0 °C, add dropwise 21.9 ml (130 mmol) trifluoromethanesulfonic anhydride [358-23-6], stir for 15 min at 0 °C and then for 16 h at room temperature. Hydrolyze by adding 200 g of ice, wash the combined organic phases twice with 150 ml of water and once with 100 ml of saturated brine, and then dry over magnesium sulfate. Filter off the desiccant and concentrate the filtrate to dryness. Yield: 61.5 g (95 mmol), 95%; purity: approximately 97% by 1< H-NMR.f) Step 200:

[0107]

[0108] A well-stirred mixture of 64.5 g (100 mmol) 200e, 50.8 g (200 mmol) bis(pinacolato)diborane [73183-34-3], 29.5 g (300 mmol) potassium acetate, anhydrous [127-08-2], 200 g glass spheres (3 mm diameter knife), 3.7 g (5 mmol) bis(tricyclohexylphosphino)palladium(II) chloride [29934-17-6], and 1500 ml dioxane is stirred for 18 h at 100 °C. Filter off while still warm over a Celite bed pre-slurried with dioxane, concentrate the filtrate in vacuo, collect the residue in 500 ml DCM, wash the organic phase twice with 300 ml water and once with 200 ml saturated brine, and dry over magnesium sulfate. Add 100 ml of EA, draw off over a silica gel bed pre-slurried with DCM:EA (3:1, vv), concentrate the filtrate to dryness and chromatograph (Torrent automatic column machine from Semrau) the residue stand. Yield: 50.5 g (76 mmol) 76 %; purity: approx. 97 % by 1< H-NMR.B) Synthesis of ligands L: Example L1: A) L1A:

[0109]

[0110] To a well-stirred solution of 53.7 g (100 mmol) S100 in 500 ml acetonitrile and 4.3 ml (105 mmol) methanol, add 13.8 g (100 mmol) potassium carbonate and 100 g glass beads at room temperature. After weakly exothermic reaction, stir for 1 h more, add 30.5 g (100 mmol) S1, 20.7 g (150 mmol) potassium carbonate, 1.91 g (4 mmol) X-Phos and 449 mg (2 mmol) palladium(II) acetate and stir for 16 h under reflux. Aspirate while still warm over a Celite bed pre-slurried with acetonitrile, condense the filtrate in vacuo at 40 °C, take up the reflux in 600 ml DCM, wash three times each with 200 ml water and once with 200 ml brine, and dry over magnesium sulfate. Add 200 ml EA, filter off over a silica gel bed pre-slurried with DCM / EA (4:1 vv), concentrate the filtrate to about 150 ml in vacuo, aspirate from the precipitated product, wash three times with 100 ml methanol each, and dry in vacuo at 40 °C. Yield: 52.0 g (71 mmol), 71 %; purity: ca. 97 % by 1< H NMR.B) L1:

[0111]

[0112] Hydrogenate 73.3 g (100 mmol) L1A in a mixture of 500 ml THF and 300 ml MeOH with the addition of 2 g palladium (5 wt%) on charcoal and 16.1 g (300 mmol) NH 4 Cl at 40 °C under 1.5 bar hydrogen atmosphere until hydrogen uptake is completed (about 12 h). Filter from the catalyst over a Celite bed pre-slurried with THF, remove the solvent in vacuo and flash-chromatograph the residue on an automated column (CombiFlashTorrent from A Semrau). Yield: 55.4 g (75 mmol), 75%; purity: approximately 97% by 1< H-NMR.

[0113] Analogously, the deuteration of the alkyne can also be carried out using deuterium D 2 , H 3 COD and ND 4 Cl, obtaining -CD 2 -CD 2 bridges instead of-CH 2 -CH 2 bridges.

[0114] Analogously, the following compounds can be prepared in yields of about 40-60%: Ex.EductsProductL2S1 S101L3S2 S101L4S3 S101L5S4 S101L6S5 S101L7S6 S101L8S7 S101L9S8 S101L10S9 S101L11S10 S101L12S11 S101L13S12 S101L14S13 S101L15S14 S101L16S15 S101L17S16 S101L18S17 S101L19S18 S101L20S19 S101L21S2 S102L22S3 S102L23S10 S102L24S14 S102L25S1 S103L26S2 S103L27S3 S103L28S4 S103L29S5 S103L30S6 S103L31S7 S103L32S8 S103L33S9 S103L34S10 S103L35S11 S103L36S12 S103L37S13 S103L38S14 S103L39S15 S103L40S16 S103L41S17 S103L42S18 S103L43S19 S103L44S1 S104L45S2 S104L46S3 S104L47S4 S104L48S5 S104L49S6 S104L50S7 S104L51S8 S104L52S9 S104L53S10 S104L54S11 S104L55S12 S104L56S13 S104L57S14 S104L58S15 S104L59S16 S104L60S17 S104L61S18 S104L62S19 S104L63S2 S105L64S3 S105L65S4 S105L66S5 S105L67S6 S105L68S10 S105L69S14 S105L70S15 S105L71S16 S105L72S17 S105L73S18 S105L74S19 S105L75S20 S101L76S21 S101L77S2 S106L78S10 S106L-Ref-D3Ref-S1 S101L79S2 S300L80S20 S300 C) Synthesis of iridium complexes:

[0115] The iridium complexes can be prepared, for example, according to the methods described in WO 2016 / 124304 or WO 2021 / 013775.Example Ir1:

[0116]

[0117] A mixture of 7.37 g (10 mmol) L1, 7.42 g (10 mmol) tris(2,2,6,6-tetramethyl-3,5-heptanedionato-κO 3< ,κO 5< )-iridium [99581-86-9], 50 g hydroquinone [123-31-9], and 50 g 2,6-diisopropylphenol [2078-54-8] is placed in a 500 mL two-necked round-bottom flask with a glass-jacketed magnetic core. The flask is equipped with a water separator (for media of lower density than water) and an air cooler with argon overlay. The flask is placed in a metal heating dish. The apparatus is purged with argon from above via the argon overlay for 15 min, allowing the argon to flow out of the side neck of the two-necked flask. Insert a glass-jacketed Pt-100 thermocouple into the flask via the side neck of the two neck flask and place the end just above the magnetic stirrer core.

[0118] The apparatus is then thermally insulated with several loose wraps of household aluminum foil, with the insulation extending to the center of the riser tube of the water separator. The apparatus is then rapidly heated with a laboratory heating stirrer to 245-250 °C as measured by the Pt- 100 thermal probe immersed in the molten, stirred reaction mixture. During the next 1.5 h, the react ion mixture is kept at 245-250 °C, with condensate distilling off and collecting in the water separator, and tempering from time to time. After 1.5 h, allow to cool to about 100 °C and then slowly add 300 ml of ethanol (EtOH). The yellow suspension obtained is filtered through a reverse frit, the yellow solid is washed three times with 30 ml EtOH and then dried in vacuo. The solid thus obtained is dissolved in 1000 ml of dichloromethane and filtered over 800 g of silica gel pre-slurried with dichloromethane (column diameter about 12 cm) with exclusion of air and light. The core fraction is cut out and concentrated at the rotary evaporator, with EtOH being added continuously at the same time until crystallization. After aspiration, washing with a little EtOH and drying in vacuo, further purification of the yellow product is carried out by continuous hot extraction twice with dichloromethane / iso-propanol 2:1 (vv) and then hot extraction four times with dichloromethane / acetonitrile 1:1 (vv) (prefilled amount in each case approx. 200 ml, extraction sleeve: standard cellulose Soxhlet sleeves from Whatman) under careful air and light from closure. Finally, the product is fractionally sublimed under high vacuum. Yield: 6.59 g (7.1 mmol), 71 %; purity: > 99.9 % by HPLC.Example Ir10:

[0119]

[0120] A 500 ml four-neck flask with KPG stirrer, water separator (10 ml reservoir), reflux condenser and argon overlay is charged under argon atmosphere with 7.42 g (10 mmol) L10, 3.69 g (10 mmol) iridium(III) acetate Ir(OAc) 3 , 40 g salicylic acid and 40 ml mesitylene and heated for 22 h under low reflux (internal temperature about 158 °C). The initially blue solution becomes a yellow suspension with time, except that some acetic acid initially precipitates, which is drained off. After 22 h, the solution is allowed to cool to 90 °C, 200 ml ethanol is carefully added, allowed to cool to 40 °C while stirring, the yellow solid is removed by suction, washed three times with 30 ml ethanol each time and dried in vacuo. The resulting solid is dissolved in 1000 ml dichloromethane and filtered over 800 g silica gel pre-slurried with dichloromethane (column diameter approx. 12 cm) with exclusion of air and light. The core fraction is removed and concentrated at the rotary evaporator, with EtOH being continuously added at the same time until crystallization. After aspiration, washing three times with 30 ml EtOH and drying in vacuo, further purification of the yellow product is carried out by continuous hot extraction twice with dichloromethane / iso-propanol 2:1 (vv) and then hot extraction four times with dichloromethane / acetonitrile 1:1 (VV) (reference quantity in each case approx. 200 ml, extraction sleeve: standard cellulose Soxhlet sleeves from Whatman) under careful air and light from closure. Finally, the product is fractionally sublimed under high vacuum at p ~ 10 -6< mbar and T ~ 340 °C. Yield: 7.73 g (8.3 mmol), 83 %. Purity: > 99.9 % by HPLC.

[0121] The metal complexes usually occur as a 1:1 mixture of the A and Δ isomers / enantiomers according to the procedures used above. The figures of complexes listed below usually show only one isomer. If ligands with three different partial ligands are used, or if chiral ligands are used as racemates, the derived metal complexes are obtained as a diastereomeric mixture. These can be separated by fractional crystallization or chromatographically, e.g., with a column auto mate (CombiFlash from A. Semrau). If chiral ligands are used enantiopure, the derived metal complexes accrue as a diastereomeric mixture, whose separation by fractional crystallization or chromatography leads to pure enantiomers. The separated diastereomers or enantiomers can be further purified as described above, e.g., by hot extraction.

[0122] Similarly, the following compounds can be prepared in yields of about 60-90%: Ex.LigandProductIr2L2 Ir3L3 Ir4L4 Ir5L5 Ir6L6 Ir7L7 Ir8L8 Ir9L9 Ir11L11 Ir12L12 Ir13L13 Ir14L14 Ir15L15 Ir16L16 Ir17L17 Ir18L18 Ir19L19 lr20L20 Ir21L21 Ir22L22 Ir23L23 Ir24L24 Ir25L25 Ir26L26 Ir27L27 Ir28L28 Ir29L29 Ir30L30 Ir31L31 Ir32L32 Ir33L33 Ir34L34 Ir35L35 Ir36L36 Ir37L37 Ir38L38 Ir39L39 Ir40L40 Ir41L41 Ir42L42 Ir43L43 Ir44L44 Ir45L45 Ir46L46 Ir47L47 Ir48L48 Ir49L49 Ir50L50 Ir51L51 Ir52L52 Ir53L53 Ir54L54 Ir55L55 Ir56L56 Ir57L57 Ir58L58 Ir59L59 Ir60L60 Ir61L61 Ir62L62 Ir63L63 Ir64L64 Ir65L65 Ir66L66 Ir67L67 Ir68L68 Ir69L69 Ir70L70 Ir71L71 Ir72L72 Ir73L73 Ir74L74 Ir75L75 Ir76L76 Ir77L77 Ir78L78 Ref-D3L-Ref-D3 Ir79L79 Ir80L80 D) Deuteration of the iridium complexes

[0123] The non-deuterated or partially deuterated iridium complexes can be further deuterated according to WO 2019 / 158453. The exact degree of deuteration can be followed spectroscopically by 1< H NMR spectroscopy or mass spectrometry. Each proton of the C1-symmetric iridium complexes has its own exchange kinetics, which depends on the reaction temperature and reaction time. In the structures shown below, deuterated alkyl positions with a degree of deuteration of about 90% or greater or deuterated aryl positions with a degree of deuteration of about 80% or greater are indicated by the element symbol D; individual further positions may also be partially deuterated.Example Ir100:

[0124]

[0125] Carried out analogously to V. Salamanca, Eur. J. Org. Chem. 2020, 3206.

[0126] A well-stirred mixture of 926.4 mg (1.0) mmol of the clean complex Ir1 (purity > 99.9%), 425 mg (2.0 mmol) of tripotassium phosphate, anhydrous, 20 g of glass beads (1.5 mm diameter) and 100 ml of DMSO-D6 (degree of deuteration > 99.8%) is stirred at 100 - 120 °C for 10 - 20 h until the desired degree of deuteration (monitoring via 1< H-NMR) is achieved. Instead of tripotassium phosphate, anhydrous, cesium carbonate, anhydrous can also be used in catalytic amount (10-20 mol %) at temperatures of 70 - 100 °C, selectively exchanging the aromatic positions on the dibenzofuran ortho to the -CN or -F group. Then cool using a cold water bath, add dropwise from about 60 °C 6 ml 1N acetic acid-D1 in 12 ml D 2 O, and then 200 ml water (H 2 O), allow to cool to room temperature, stir for 5 h, aspirate from the solid and wash three times with 10 ml each of H 2 O / EtOH (1:1, vv) and then three times with 10 ml each of EtOH and dry in vacuo. The solid is dissolved in DCM, the solution is filtered over silica gel, the core fraction is cut out and confined on the rotary steamer, while at the same time EtOH is continuously added until crystallization. After aspiration, washing with a little EtOH and drying in vacuo, the yellow product is further purified by continuous hot extraction four times with dichloromethane / acetonitrile 1:1 (vv) (prefilled volume approx. 30 ml each, extraction sleeve: standard Soxhlet sleeves made of cellulose from Whatman) under careful air and light from closure. Finally, the product is fractionally sublimed under high vacuum. Yield: 813.2 mg (0.87 mmol), 87 %. Purity: > 99.9 % by HPLC.

[0127] Similarly, the following compounds can be prepared in yields of about 70-90%: Ex.EductProductIr101Ir2 Ir102Ir3 Ir103Ir4 Ir104Ir5 Ir105Ir6 Ir106Ir7 Ir107Ir8 Ir108Ir9 Ir109Ir10 Ir110Ir11 Ir111Ir12 Ir112Ir13 Ir113Ir14 Ir114Ir15 Ir115Ir16 Ir116Ir17 Ir117Ir18 Ir118Ir19 Ir119lr20 Ir120Ir21 Ir121Ir22 Ir122Ir23 Ir123Ir24 Ir124Ir25 Ir125Ir26 Ir126Ir27 Ir127Ir28 Ir128Ir29 Ir129Ir30 Ir130Ir31 Ir131Ir32 Ir132Ir33 Ir133Ir34 Ir134Ir35 Ir135Ir36 Ir137Ir37 Ir137Ir38 Ir138Ir39 Ir139Ir40 Ir140Ir41 Ir141Ir42 Ir142Ir43 Ir143Ir44 Ir144Ir45 Ir145Ir46 Ir146Ir47 Ir147Ir48 Ir148Ir49 Ir149Ir50 Ir150Ir51 Ir151Ir52 Ir152Ir53 Ir153Ir54 Ir154Ir55 Ir155Ir56 Ir156Ir57 Ir157Ir58 Ir158Ir59 Ir159Ir60 Ir160Ir61 Ir161Ir62 Ir162Ir63 Ir163Ir64 Ir164Ir65 Ir165Ir66 Ir166Ir67 Ir167Ir68 Ir168Ir69 Ir169Ir70 Ir170Ir71 Ir171Ir72 Ir172Ir73 Ir173Ir74 Ir174Ir75 Ir175Ir76 Ir176Ir77 Ir177Ir78 Ir178Ir79 Ir179Ir80 Example: Luminescence properties

[0128] Figure 1 shows the photoluminescence spectrum (ca. 10 -5< M in degassed toluene) of compound Ir3 according to the invention and the reference emitters Ref-D1, Ref-D2 and Ref-D3, whose structure is shown in Table 3 below. As can be clearly seen, the compound according to the invention exhibits a significantly narrower emission spectrum compared to the reference compounds.

[0129] Figure 2 shows the photoluminescence spectra (ca. 10 -5< M in degassed toluene) of compounds Ir3, Ir178, Ir179 according to the invention and the reference emitter Ref-D3, whose structure is shown in Table 3 below. As can be clearly seen, the compounds according to the invention exhibit a significantly narrower emission spectrum compared to the reference compound.Example: Production of the OLEDs Vacuum Processed Devices:

[0130] OLEDs according to the invention as well as OLEDs according to the prior art are manufactured by a general process according to WO 2004 / 058911, which is adapted to the conditions described here (layer thickness variation, materials used).

[0131] In the following examples the results of different OLEDs are presented. Cleaned glass plates (cleaning in Miele laboratory dishwasher, cleaner Merck Extran) coated with structured ITO (Indium Tin Oxide) of thickness 50 nm are pretreated with UV-ozone for 25 minutes (UV-ozone generator PR-100, company UVP). These coated glass plates form the substrates onto which the OLEDs are deposited.

[0132] All materials are thermally evaporated in a vacuum chamber. The emission layer always consists of at least one or more matrix materials M and one of the phosphorescent dopants Ir according to the invention, which is added to the matrix material(s) by co-evaporation in a -certain volume fraction. A specification such as M1:M2:lr (55%:35%:10%) means here that the material M1 is present in the layer in a volume fraction of 55%, M2 in a volume fraction of 35% and Ir in a volume fraction of 10%. Similarly, the electron transport layer consists of a mixture of two materials. The exact structure of the OLEDs can be seen in Table 1. The materials used to fabricate the OLEDs are shown in Table 3.

[0133] The OLEDs are characterized as standard. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd / A), the power efficiency (measured in lm / W) and the external quantum efficiency (EQE, measured in %) are determined as a function of the luminance, calculated from current-voltage-luminance curves (IUL curves) assuming a Lambertian radiation pattern, and the lifetime. The efficiency in cd / A, the EQE in %, the voltage in V, the color coordinates CIE, the maximum of the electroluminescence spectrum λ max in nm and the spectral half width (FWHM: Full Width Half Maximum) of the electroluminescence spectrum in eV are specified at a luminance of 1000 cd / m 2< .The OLEDs have the following layer structure:

[0134] Substrate Hole injection layer (HIL) of HTM1 doped with 5 % NDP-9 (commercially available from Novaled), 20 nm Hole transport layer (HTL), see Table 1 Electron blocking layer (EBL), see Table 1 Emission Layer (EML), see Table 1 Hole blocking layer (HBL), see Table 1 Electron transport layer (ETL), made of ETM1:ETM2 (50%:50%), 30 nm Electron injection layer (EIL) made of ETM2, 1 nm Aluminum cathode, 100 nm Table 1: Structure of phosphorescent OLED devices Ex. HTL Thickness EBL Thickness EML Thickness HBL Thickness GP1HTM1 40 nmEBM1 20 nmM1:M2:Ir3 (46%:46%:8%) 40 nmHBM1 5 nmGP2HTM1 40 nmEBM1 20 nmM1:M2:Ir178 (46%:46%:8%) 40 nmHBM1 5 nmGP3HTM1 40 nmEBM1 20 nmM1:M2:Ir179 (46%:46%:8%) 40 nmHBM1 5 nm Table 2: Results phosphorescent OLED devices Ex. Eff. [cd / A] EQE (%) Voltage (V) CIE (x / y) λ max (nm) FWHM (eV) GP191.323.52.790.33 / 0.645260.14GP2100.025.52.620.33 / 0.645260.14GP394.424.82.830.30 / 0.665220.13 Table 3: Structural formulae of the materials used HTM1 EBM11365840-52-31450933-44-4 M1 M21822310-86-01643479-47-3 HBM1 ETM11955543-57-31819335-36-8 ETM225387-93-3 Ref-D1 Ref-D22458813-55-11609368-32-2 Ref-D3

Claims

1. A compound of formula (1),         Ir(L)     Formula (1) wherein the ligand L has a structure of formula (2): wherein the ligand L coordinates to the iridium atom via the positions marked with * and wherein the hydrogen atoms not explicitly shown may also be partially or completely replaced by deuterium, and wherein the symbols and indices used apply: R at each occurrence is the same or different and is F or CN; Ar is a phenyl or biphenyl group which may be unsubstituted or substituted by one or more radicals, each of which are the same or different and are selected from the group consisting of F, CN, Si(CH3)3 , a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms or a cyclic alkyl group having 4 to 8 C atoms; in this case the phenyl or biphenyl group or the substituents on this phenyl or biphenyl group are optionally partially or completely deuterated; R1 at each occurrence is the same or different and is F, CN, a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms, a cyclic alkyl group having 4 to 8 C atoms, phenyl or biphenyl, wherein R1 is optionally partially or completely deuterated; and wherein when two adjacent radicals R1 represent a straight-chain, branched or cyclic alkyl group, the two radicals R1 may form a ring system with one another; R2, R3 at each occurrence is the same or different and is F, a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms or a cyclic alkyl group having 4 to 8 C atoms; wherein R2 and R3 are optionally partially or completely deuterated; and wherein two adjacent radicals R2 or two adjacent radicals R3 may form a ring system with one another; R4 at each occurrence is the same or different and is a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms, a cyclic alkyl group having 4 to 8 C atoms, phenyl or biphenyl, wherein R4 is optionally partially or completely deuterated; wherein when two adjacent radicals R4 represent a straight-chain, branched or cyclic alkyl group, the two radicals R4 may form a ring system with one another; R5 at each occurrence is the same or different and is a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms or a cyclic alkyl group having 4 to 8 C atoms; wherein R5 is optionally partially or fully deuterated; wherein two adjacent radicals R5 may form a ring system with one another; R6, R7 at each occurrence is the same or different and is H, D, CH3 or C2H5 , wherein the CH3 group or the C2H5 group is optionally partially or completely deuterated; r is 1 or 2; s is 0 or 1; m at each occurrence is the same or different and is 0, 1, 2, 3 or 4; n, o at each occurrence of is the same or different and is 0, 1, 2, or 3; p is 0, 1 or 2; q is 0, 1, 2, or 3; with the proviso that the sum of q + r + s ≤ 4.

2. The compound according to claim 1, characterized in that r = 1 and the ligand L has a structure according to formula (3), (4), (5) or (6), wherein the symbols and indices used have the meanings given in claim 1 and the hydrogen atoms not explicitly shown may also be partially or completely replaced by deuterium.

3. The compound according to claim 1 or 2, characterized in that R = CN and s = 0; or that R = F and s = 1; or that R = F, s = 0 and q = 1, wherein R5 represents a cyclopentyl or cyclohexyl group which is optionally partially or completely deuterated.

4. The compound according to any one of claims 1 to 3, characterized in that the ligand L has a structure according to one of the formulae (7), (8), (9) or (10), wherein the symbols and indices used have the meanings given in claim 1 and the hydrogen atoms not explicitly shown may also be partially or completely replaced by deuterium.

5. The compound of any one of claims 1 to 4, characterized in that the ligand L has a structure of formula (11a), (11b) or (11c), wherein the symbols and indices used have the meanings given in claim 1, the hydrogen atoms not explicitly shown may also be partially or completely replaced by deuterium, R6 is H, D, CH3 or CD3; and R5 in formula (11c) preferably is a cyclopentyl or cyclohexyl group which is optionally partially or completely deuterated.

6. The compound of any one of claims 1 to 5, characterized in that a deuterium atom is bonded in all ortho-positions to R in which Ar or R5 is not bonded.

7. The compound according to any one of claims 1 to 6, characterized in that the ligand L is selected from the structures of formulae (11a-1), (11b-1) or (11c-1), wherein the symbols and indices used have the meanings given in claim 1, the hydrogen atoms not explicitly shown may also be partially or completely replaced by deuterium, each occurrence of R6 is the same or different and represents H, D, CH3 or CD3; and R5 in formula (11c-1) preferably represents a cyclopentyl or cyclohexyl group which is optionally partially or completely deuterated.

8. The compound according to any one of claims 1 to 7, characterized in that Ar is a phenyl group which is optionally partially or fully deuterated and which is otherwise unsubstituted or substituted by a methyl group which is optionally partially or fully deuterated.

9. The compound according to any one of claims 1 to 8, characterized in that the symbols and indices are: Ar is a phenyl group which is optionally partially or fully deuterated and which is optionally substituted by a methyl group which is partially or fully deuterated; R1 at each occurrence is the same or different and is selected from the group consisting of CN, a straight chain alkyl group having 1 to 4 C atoms, a branched alkyl group having 3 to 5 C atoms, a cyclic alkyl group having 5 or 6 C atoms, or a phenyl group, each of which groups is optionally partially or fully deuterated; R2, R3 at each occurrence is the same or different and is selected from the group consisting of a straight chain alkyl group having 1 to 4 C atoms, a branched alkyl group having 3 to 5 C atoms, or a cyclic alkyl group having 5 or 6 C atoms, each of which groups are optionally partially or fully deuterated; R4 at each occurrence is the same or different and is selected from the group consisting of a straight chain alkyl group having 1 to 4 C atoms, a branched alkyl group having 3 to 5 C atoms, a cyclic alkyl group having 5 or 6 C atoms, or phenyl, each of which groups are optionally partially or fully deuterated; R5 each occurrence is the same or different and is selected from the group consisting of a straight chain alkyl group having 1 to 4 C atoms, a branched alkyl group having 3 to 5 C atoms, or a cyclic alkyl group having 5 or 6 C atoms, each of which groups are optionally partially or fully deuterated; R6 at each occurrence is the same or different and is H, D, or CH3 , which is optionally partially or fully deuterated; R7 at each occurrence is the same or different and is H or D; m at each occurrence of is the same or different and is 0, 1, 2 or 3; n, o at each occurrence of is the same or different and is 0, 1 or 2; p is 0 or 1; q is 0 or 1; s is 0 for R = CN and is 1 for R = F.

10. A process for preparing a compound according to any one of claims 1 to 9 comprising the step of reacting the free ligand with an iridium alkoxide, an iridium ketoketonate, an iridium halide or an iridium carboxylate.

11. A formulation comprising at least one compound according to any one of claims 1 to 9 and at least one further compound, wherein the further compound is selected from a solvent and / or a matrix material.

12. A use of a compound according to one or more of claims 1 to 9 in an electronic device, or for generating singlet oxygen, or in photocatalysis.

13. A photocatalyst comprising at least one compound according to any one of claims 1 to 9.

14. An electronic device comprising at least one compound according to any one of claims 1 to 9.

15. The electronic device of claim 14, characterized in that it is an organic electroluminescent device and the compound of any one of claims 1 to 9 is used as an emitting compound in one or more emitting layers.