Metal complexes

1. A compound of formula (1)

Ir(L) n (L′) m   (1)

comprising a substructure M(L) n of one of formula (8) or (9):

wherein

HetAr is a group of formula (HetAr):

wherein the dotted bond indicates the bond of this group to the ligand or to Ar;

Y is the same or different in each instance and is CR 2 or N, with the proviso that at least two and at most three Y groups are N and that not more than two nitrogen atoms are bonded directly to one another;

X in each instance is CR 1 or N, with the proviso that not more than two X groups per cycle are N or two X groups bonded directly to one another are a group of formula (3) or two adjacent X groups on the two different cycles are a group of formula (4):

 wherein the dotted bonds indicate the linkage of this group in the ligand;

Z in each instance is CR 1 or N, with the proviso that not more than two Z groups are N;

Ar is a para-phenylene group optionally substituted by one or more R 1 radicals;

R 1 in the substructure comprising formula (8) or (9) is the same or different in each instance and is H, D, Cl, Br, I, N(R 3 ) 2 , CN, NO 2 , OH, COOH, C(═O)N(R 3 ) 2 , B(OR 3 ) 2 , C(═O)R 3 , P(═O)(R 3 ) 2 , S(═O)R 3 , S(═O) 2 R 3 , OSO 2 R 3 , a straight-chain alkyl, alkoxy, or thioalkoxy 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, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, each of which is optionally substituted by one or more R 3 radicals, wherein one or more nonadjacent CH 2 groups are optionally replaced by R 3 C═CR 3 , C≡C, Si(R 3 ) 2 , C═O, NR 3 , O, S, or CONR 3 and wherein one or more hydrogen atoms are optionally replaced by D, Cl, Br, I, or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and is optionally substituted by one or more R 3 radicals, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 3 radicals, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 3 radicals, or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group having 10 to 40 aromatic ring atoms and is optionally substituted by one or more R 3 radicals; and wherein, two adjacent R 1 radicals or two adjacent R 2 radicals together optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system;

R 2 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R 3 ) 2 , CN, NO 2 , OH, COOH, C(═O)N(R 3 ) 2 , Si(R 3 ) 3 , B(OR 3 ) 2 , C(═O)R 3 , P(═O)(R 3 ) 2 , S(═O)R 3 , S(═O) 2 R 3 , OSO 2 R 3 , a straight-chain alkyl, alkoxy, or thioalkoxy 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, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, each of which is optionally substituted by one or more R 3 radicals, wherein one or more nonadjacent CH 2 groups are optionally replaced by R 3 C═CR 3 , Si(R 3 ) 2 , C═O, NR 3 , O, S, or CONR 3 and wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and is optionally substituted by one or more R 3 radicals, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 3 radicals, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 3 radicals, or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group having 10 to 40 aromatic ring atoms and is optionally substituted by one or more R 3 radicals; and wherein, two adjacent R 1 radicals or two adjacent R 2 radicals together optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system;

R 3 is the same or different in each instance and is H, D, F, or an aliphatic, aromatic, and/or heteroaromatic group having 1 to 20 carbon atoms, wherein one or more hydrogen atoms is optionally replaced by F; and wherein two or more R 3 substituents together optionally define a mono- or polycyclic aliphatic ring system;

L′ is the same or different in each instance and is a bidentate, monoanionic ligand, wherein L′ in a compound comprising formula (8) or (9) is a monoanionic bidentate ligand bonded to the iridium via one nitrogen atom and one carbon atom or via two oxygen atoms or via two nitrogen atoms or via one nitrogen atom and one oxygen atom;

n is 1, 2, or 3;

m is (3−n);

p is 0 or 1.

2. The compound of claim 1 , wherein not more than one X group per cycle is N and not more than one Z group is N.

3. The compound of claim 1 , wherein the substructure M(L) n is selected from the group consisting of formulae (8a) and (9a):

4. The compound of claim 1 , wherein, in compounds containing a substructure of formula (8), n=2 and L′ is a non-ortho-metalated ligand and, in compounds containing a substructure of formula (9), n=3 or n=2 and L′ is an ortho-metalated ligand.

5. The compound of claim 4 , wherein L′ is a diketonate.

6. The compound of claim 3 , wherein, in compounds containing a substructure of (8a), n=2 and L′ is a non-ortho-metalated ligand and, in compounds containing a substructure of formula (9a), n=3 or n=2 and L′ is an ortho-metalated ligand.

7. The compound of claim 6 , wherein L′ is a diketonate.

8. The compound of claim 1 , wherein (HetAr) is selected from the group consisting of groups of formulae (HetAr-1) through (HetAr-4):

9. The compound of claim 1 , wherein the R 2 radicals are the same or different in each instance and are selected from the group consisting of H, D, or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which are optionally substituted by one or more R 3 radicals.

10. The compound of claim 1 , wherein (HetAr) is selected from the group consisting of groups of formulae (HetAr-1a) through (HetAr-4a):

wherein R 2 is the same or different in each instance and is an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which are optionally substituted by one or more R 3 radicals.

11. The compound of claim 1 , wherein the R 1 radicals are the same or different in each instance and are selected from the group consisting of H, D, F, N(R 3 ) 2 , CN, B(OR 3 ) 2 , C(═O)R 3 , 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 is optionally substituted by one or more R 3 radicals, wherein one or more hydrogen atoms are optionally replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which are optionally substituted by one or more R 3 radicals; and wherein two adjacent R 1 radicals together optionally define a mono- or polycyclic, aliphatic or aromatic ring system.

12. A process for preparing the compound of claim 1 comprising (1) reacting said compound with a HetAr-Hal group, wherein said compound has a reactive leaving group rather than the HetAr group and wherein Hal is F, Cl, Br, or I or (2) reacting the free ligands 1 and optionally L′ with an iridium alkoxide of formula (40), an iridium ketoketonate of formula (41), an iridium halide of formula (42), a dimeric iridium complex of formula (43), an iridium complex of formula (44), or an iridium compound bearing both alkoxide and/or halide and/or hydroxyl radicals and ketoketonate radicals:

wherein Hal=F, Cl, Br, or I, L″ is an alcohol or a nitrile, and (Anion) is a non-coordinating anion.

13. A formulation comprising at least one compound of claim 1 and at least one solvent and/or a further organic or inorganic compound.

14. An electronic device comprising at least one compound of claim 1 .

15. The electronic device of claim 14 , wherein the electronic device is an organic electroluminescent device and the compound is used as emitting compound in one or more emitting layers.

16. A compound of formula (1)

Ir(L) n (L′) m   (1)

comprising a substructure M(L) n of one of formula (5), (6), (7a)′:

wherein

HetAr is a group of formula (HetAr):

wherein the dotted bond indicates the bond of this group to the ligand or to Ar;

Y is the same or different in each instance and is CR 2 or N, with the proviso that at least two and at most three Y groups are N and that not more than two nitrogen atoms are bonded directly to one another;

X in each instance is CR 1 or N, with the proviso that not more than two X groups per cycle are N or two X groups bonded directly to one another are a group of formula (3) or two adjacent X groups on the two different cycles are a group of formula (4):

wherein the dotted bonds indicate the linkage of this group in the ligand;

Z in each instance is CR 1 or N, with the proviso that not more than two Z groups are N;

Ar is a para-phenylene group optionally substituted by one or more R 1 radicals;

R 1 in the substructure comprising formula (5), (6) is the same or different in each instance and is H, D, Cl, Br, I, N(R 3 ) 2 , CN, NO 2 , OH, COOH, C(═O)N(R 3 ) 2 , B(OR 3 ) 2 , C(═O)R 3 , P(═O)(R 3 ) 2 , S(═O)R 3 , S(═O) 2 R 3 , OSO 2 R 3 , a straight-chain alkyl, alkoxy, or thioalkoxy 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, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, each of which is optionally substituted by one or more R 3 radicals, wherein one or more nonadjacent CH 2 groups are optionally replaced by R 3 C═CR 3 , C≡C, Si(R 3 ) 2 , C═O, NR 3 , O, S, or CONR 3 and wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and is optionally substituted by one or more R 3 radicals, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 3 radicals, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 3 radicals, or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group having 10 to 40 aromatic ring atoms and is optionally substituted by one or more R 3 radicals; and wherein, two adjacent R 1 radicals or two adjacent R 2 radicals together optionally define a mono- or polycyclic, aliphatic, aromatic, or heteroaromatic ring system;

R 1 in the substructure comprising formula (7a)′ is the same or different in each instance and is H, D, Cl, Br, I, N(R 3 ) 2 , CN, NO 2 , OH, COOH, C(═O)N(R 3 ) 2 , B(OR 3 ) 2 , C(═O)R 3 , P(═O)(R 3 ) 2 , S(═O)R 3 , S(═O) 2 R 3 , OSO 2 R 3 , a straight-chain alkyl, alkoxy, or thioalkoxy 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, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, each of which is optionally substituted by one or more R 3 radicals, wherein one or more nonadjacent CH 2 groups are optionally replaced by R 3 C═CR 3 , C≡C, Si(R 3 ) 2 , C═O, NR 3 , O, S, or CONR 3 and wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, or CN, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and is optionally substituted by one or more R 3 radicals, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 3 radicals, an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 3 radicals, or a diarylamino group, diheteroarylamino group, or arylheteroarylamino group having 10 to 40 aromatic ring atoms and is optionally substituted by one or more R 3 radicals;

R 2 is the same or different in each instance and is H, D, F, Cl, Br, I, N(R 3 ) 2 , CN, NO 2 , OH, COOH, C(═O)N(R 3 ) 2 , Si(R 3 ) 3 , B(OR 3 ) 2 , C(═O)R 3 , P(═O)(R 3 ) 2 , S(═O)R 3 , S(═O) 2 R 3 , OSO 2 R 3 , a straight-chain alkyl, alkoxy, or thioalkoxy 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, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, each of which is optionally substituted by one or more R 3 radicals, wherein one or more nonadjacent CH 2 groups are optionally replaced by R 3 C═CR 3 , C≡C, Si(R 3 ) 2 , C═O, NR 3 , O, S, or CONR 3 and wherein one or more hydrogen atoms are optionally replaced by D, F, Cl, Br, I, or CN, an aromatic ring system having 5 to 60 aromatic ring atoms consisting of 6 to 60 carbon atoms in the ring system and is optionally substituted by one or more R 3 radicals, an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 3 radicals, or an aralkyl group having 5 to 40 aromatic ring atoms and is optionally substituted by one or more R 3 radicals; and wherein, two adjacent R 2 radicals together optionally define a mono- or polycyclic, aliphatic, or aromatic, ring system;

R 3 is the same or different in each instance and is H, D, F, or an aliphatic, and/or aromatic group having 1 to 20 carbon atoms, wherein one or more hydrogen atoms is optionally replaced by F; and wherein two or more R 3 substituents together optionally define a mono- or polycyclic aliphatic ring system;

L′ is the same or different in each instance and is a bidentate, monoanionic ligand, wherein L′ in a compound comprising formula (5) is a bidentate, monoanionic ligand bonded to the iridium via two oxygen atoms or via two nitrogen atoms or via one nitrogen atom and one oxygen atom, and wherein L′ in a compound comprising formula (6), or (7a)′ is a monoanionic bidentate ligand bonded to the iridium via one nitrogen atom and one carbon atom or via two oxygen atoms or via two nitrogen atoms or via one nitrogen atom and one oxygen atom;

n is 1, 2, or 3;

m is (3−n);

p is 0 or 1 in formula (6), (7a)′, and

p is 1 in formula (5).

17. The compound of claim 16 , wherein the R 2 radicals are the same or different in each instance and are selected from the group consisting of H, D, or an aromatic ring system having 6 to 24 aromatic ring atoms, which are optionally substituted by one or more R 3 radicals.

18. The compound of claim 16 , wherein (HetAr) is selected from the group consisting of groups of formulae (HetAr-1a) through (HetAr-4a):

wherein R 1 is the same or different in each instance and is an aromatic ring system having 6 to 24 aromatic ring atoms, which are optionally substituted by one or more R 3 radicals.