Materials for organic electroluminescent devices

1. A compound of the formula (1), (2), (3a) or (3b),

where the following applies to the symbols and indices used:

Ar is on each occurrence, identically or differently, a heteroaryl group selected from the group consisting of triazine, pyrazine, pyrimidine, pyridazine, pyridine, pyrazole, imidazole, oxazole, 1,3,4-oxadiazole, benzimidazole or thiazole, each of which is optionally substituted by one or more groups R 1 ;

X is a group of the formula (4), where the dashed bond in each case indicates the bond to the two benzene rings:

or X is on each occurrence, identically or differently, a divalent bridge selected from B(Ar 2 ), C(Ar 2 ) 2 , C(Ar 1 Ar 2 ), Si(Ar 2 ) 2 , C═C(Ar 2 ) 2 or C═NAr 2 ;

X 1 is on each occurrence, identically or differently, X or a divalent bridge selected from B(R 1 ), C(R 1 ) 2 , Si(R 1 ) 2 , C═C(R 1 ) 2 , C═NR 1 , B(Ar 1 ), C(Ar 1 ) 2 , Si(Ar 1 ) 2 , C═C(Ar 1 ) 2 or C═NAr 1 ;

R 1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CHO, N(Ar 1 ) 2 , C(═O)Ar 1 , P(═O)(Ar 1 ) 2 , S(═O)Ar 1 , S(═O) 2 Ar 1 ,CR 2 ═CR 2 Ar 1 , CN, NO 2 , Si(R 2 ) 3 , B(OR 2 ) 2 , B(R 2 ) 2 , B(N(R 2 ) 2 ), OSO 2 R 2 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R 2 , where one or more, preferably non-adjacent CH 2 groups is optionally replaced by R 2 C═CR 2 , C≡C, Si(R 2 ) 2 , Ge(R 2 ) 2 , Sn(R 2 ) 2 , C═O, C═S, C═Se, C═NR 2 , P(═O)(R 2 ), SO, SO 2 , NR 2 ,O, S or CONR 2 and where one or more H atoms is optionally replaced by D, F, Cl, Br, I, CN or NO 2 , or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2 , or an aryloxy or hetero-aryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 ; two or more adjacent substituents R 1 here may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another;

Ar 1 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 ; two radicals Ar 1 which are bonded to the same nitrogen, phosphorus or boron atom may here also be linked to one another by a single bond or a bridge selected from B(R 2 ), C(R 2 ) 2 , Si(R 2 ) 2 , C═O, C═NR 2 , C═C(R 2 ) 2 , O, S, S═O, SO 2 , N(R 2 ), P(R 2 ) and P(═O)R 2 ;

R 2 is on each occurrence, identically or differently, H, D or an aliphatic, aromatic and/or heteroaromatic organic radical having 1 to 20 C atoms, in which, in addition, H atoms is optionally replaced by D or F; two or more adjacent substituents R 2 here may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another;

n is 0 or 1;

m is 0, 1,2 or 3;

o is 0, 1, 2, 3 or 4 if m=0 and is 0, 1, 2 or 3 if m=1;

p, q are on each occurrence, identically or differently, 0 or 1, with the proviso that p+q is equal to 1 or 2;

where the compound of the formula (1), (2), (3a) or (3b) contains at least one group Ar 2 , where Ar 2 is selected from a carbazole group, an azacarbazole group, a cis- or trans-indenocarbazole group, a cis- or trans-indenoazacarbazole group or a cis- or trans-indolocarbazole group, each of which is optionally substituted by one or more radicals R 1 , where two or more adjacent substituents R 1 , together with the atoms to which they are bonded, may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another, with the proviso that the group Ar 2 is not in conjugation with the group Ar.

2. The compound according to claim 1 , wherein the following applies to the symbols in the compounds of the formulae (1), (2), (3a) and (3b):

Ar is on each occurrence, identically or differently, triazine, pyrimidine or pyrazine, in particular triazine, each of which is optionally substituted by one or more radicals R 1 ;

X is on each occurrence, identically or differently, a group of the formula (4), where the dashed bond in each case indicates the bond to the two benzene rings;

X 1 is, identically or differently on each occurrence, a divalent bridge selected from C(R 1 ) 2 , Si(R 1 ) 2 or C═C(R 1 ) 2 ;

R 1 is on each occurrence, identically or differently, H, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 8 C atoms or an aromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, each of which is optionally substituted by one or more radicals R 2 , or an aryloxy or heteroaryloxy group having 5 to 20 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , or a combination of these systems; two or more adjacent substituents R 1 here may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another;

Ar 1 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 20, which is optionally substituted by one or more radicals R 2 ; two radicals Ar 1 which are bonded to the same nitrogen, phosphorus or boron atom may here also be linked to one another by a single bond or a bridge selected from C(R 2 ) 2 , C═O, O, S and N(R 2 );

R 2 is on each occurrence, identically or differently, H, D or an aliphatic, aromatic and/or heteroaromatic organic radical having 1 to 10 C atoms, in which, in addition, H atoms is optionally replaced by F; two or more adjacent substituents R 2 here may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another;

Ar 2 is on each occurrence selected from carbazole, azacarbazole, indenocarbazole and indolocarbazole, each of which may also be substituted by one or more radicals R 1 ;

the other symbols and indices have the meanings indicated in claim 1 .

3. The compound according to claim 2 , wherein

X 1 is C(R 1 ) 2 ;

Ar 1 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 10, aromatic ring atoms, which is optionally substituted by one or more radicals R 2 ; two radicals Ar 1 which are bonded to the same nitrogen, phosphorus or boron atom may here also be linked to one another by a single bond or a bridge selected from C(R 2 ) 2 , C═O, O, S and N(R 2 );

R 2 is on each occurrence, identically or differently, H, D or an aliphatic, aromatic and/or heteroaromatic organic radical having 1 to 6 C atoms, in which, in addition, H atoms is optionally replaced by F; two or more adjacent substituents R 2 here may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another.

4. The compound according to claim 1 , wherein the compound is selected from compounds of the formulae (5) to (12),

where the symbols and indices have the same meanings as described in claim 1 .

5. The compound according to claim 1 , wherein the compound is selected from compounds of the formulae (13) to (20),

where the symbols and indices have the meanings indicated in claim 1 .

6. The compound according to claim 1 , wherein the compound is selected from compounds of the formulae (21) to (28),

where the symbols and indices have the meanings indicated above, p and q are on each occurrence, identically or differently, 0 or 1, where the sum of p and q is 1 or 2, and n is 0 or 1.

7. The compound according to claim 1 , wherein the monovalent group Ar is selected from the groups of the formulae (29) to (41), where the dashed bond in each case indicates the bond from the group to the fluorene or spirobifluorene or, optionally, to Ar 1 , and R 1 has the same meaning as described in claim 1 , and in that the divalent group Ar in compounds of the formula (2) is selected from the groups of the formulae (42) to (49), where the dashed bonds in each case indicate the bond from the group to the fluorene or spirobifluorene, and R 1 has the same meaning as described in claim 1 :

8. The compound according to claim 1 , wherein the groups Ar 2 are selected from the formulae (50) to (63), where the dashed bond in each case indicates the bonding of this group in the molecule, and the other symbols and indices used have the meanings given in claim 1 :

9. A process for the preparation of the compound according to claim 1 , which comprises introducing the groups Ar and/or Ar 2 by a metal-catalysed coupling reaction.

10. A process for the preparation of the compound according to claim 1 , which comprises introducing the groups Ar and/or Ar 2 by a Suzuki coupling or Hartwig-Buchwald coupling.

11. An electronic device which comprises the compound according to claim 1 .

12. The electronic device as claimed in claim 11 , wherein the device is selected from the group consisting of organic electroluminescent device (OLED, PLED), organic integrated circuit (O—IC), organic field-effect transistor (O-FET), organic thin-film transistor (O-TFT), organic light-emitting transistor (O-LET), organic solar cell (O—SC), organic optical detector, organic photoreceptor, organic field-quench device (O-FQD), light-emitting electrochemical cell (LEC) or organic laser diode (O-laser), and said compound is in at least one layer.

13. An organic electroluminescent device which comprises the compound according to claim 1 is employed in an emission layer.

14. An organic electroluminescent device which comprises the compound according to claim 1 is employed in a matrix material for phosphorescent emitters, or in an electron-transport layer.

15. The organic electroluminescent device according to claim 12 , wherein the phosphorescent emitter is a compound of the formulae (64) to (67),

where R 1 has the same meaning as described above, and the following applies to the other symbols used:

DCy is, identically or differently on each occurrence, a cyclic group which contains at least one donor atom, via which the cyclic group is bonded to the metal, and which may in turn carry one or more substituents R 1 ; the groups DCy and CCy are connected to one another via a covalent bond;

CCy is, identically or differently on each occurrence, a cyclic group which contains a carbon atom via which the cyclic group is bonded to the metal and which may in turn carry one or more substituents R 1 ;

A is, identically or differently on each occurrence, a monoanionic, bidentate-chelating ligand.

16. The organic electroluminescent device according to claim 15 , wherein

DCy is, identically or differently on each occurrence, a cyclic group which contains at least one nitrogen, carbon in the form of a carbene or phosphorus, via which the cyclic group is bonded to the metal, and which may in turn carry one or more substituents R 1 ; the groups DCy and CCy are connected to one another via a covalent bond;

and

A is, identically or differently on each occurrence, a diketonate ligand.

17. A mixture comprising at least one phosphorescent emitter and at least one compound according to claim 1 .

18. A solution or formulation comprising at least one compound according to claim 1 and at least one solvent.

19. A solution or formulation comprising at least one compound according to claim 1 and at least one organic solvent.

20. A solution or formulation comprising said mixture according to claim 17 and at least one solvent.