Nitrogen-containing condensed heterocyclic compounds for OLEDs

1. A compound of the formula (1), formula (2), formula (3) or formula (4):

wherein the compound of the formula (1) is selected from compounds of the following formulae (11a) to (31b):

where the following applies to the symbols and indices used:

A is on each occurrence, identically or differently, CR or N;

W is C if a group Y is bonded to this group W and is CR or N if no group Y is bonded to this group W;

with the proviso that at least one symbol A and/or at least one symbol W stands for N;

X is on each occurrence, identically or differently, N, P or P═O;

Y is C(R 1 ) 2 ;

wherein one or two R groups are selected from structures of the following formulae (32) to (67):

and the other R groups stand for H or D;

Z is on each occurrence, identically or differently, CR 2 or N, with the proviso that one group Z, two groups Z or three groups Z stand for N;

Ar 1 is, identically or differently on each occurrence, a divalent aryl or heteroaryl group having 5 to 16 C atoms, which may be substituted by one or more radicals R 2 ;

m is on each occurrence, identically or differently, 0, 1, 2 or 3,

E is selected from the group consisting of C(R 2 ) 2 , NR 2 , O or S;

G is selected from the group consisting of NR 2 , O or S;

R 1 are on each occurrence, identically or differently, H, D, F, Cl, Br, I, CN, NO 2 , N(Ar) 2 , N(R 2 ) 2 , C(═O)Ar, C(═O)R 1 , P(═O)(Ar) 2 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each of which is optionally substituted by one or more radicals R 2 , where one or more 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 , an aromatic or heteroaromatic ring system having 5 to 80 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2 , an aryloxy or heteroaryloxy 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 , where two or more adjacent substituents R or two substituents R 1 which are bonded in the same group Y may optionally form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which is optionally substituted by one or more radicals R 2 , with one another;

R 2 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO 2 , N(Ar) 2 , N(R 3 ) 2 , C(═O)Ar, C(═O)R 3 , P(═O)(Ar) 2 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each of which is optionally substituted by one or more radicals R 3 , where one or more non-adjacent CH 2 groups is optionally replaced by R 3 C═CR 3 , C≡C, Si(R 3 ) 2 , Ge(R 3 ) 2 , Sn(R 3 ) 2 , C═O, C═S, C═Se, C═NR 3 , P(═O)(R 3 ), SO, SO 2 , NR 3 , O, S or CONR 3 and where one or more H atoms is optionally replaced by D, F, Cl, Br, 1, CN or NO 2 , 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 3 , an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 3 , or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, where two or more adjacent substituents R 2 may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which is optionally substituted by one or more radicals R 3 ;

R 3 is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms is optionally replaced by D, F, Cl, Br, I or CN, where two or more adjacent substituents R 3 may form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system with one another;

Ar is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5-30 aromatic ring atoms, which is optionally substituted by one or more non-aromatic radicals R 3 ; two radicals Ar here which are bonded to the same N atom or P atom may also be bridged to one another by a single bond or a bridge selected from N(R 3 ), C(R 3 ) 2 , O or S;

L is a di-, tri-, tetra-, penta- or hexavalent straight-chain alkylene, alkylidene, alkyleneoxy or thioalkyleneoxy group having 1 to 40 C atoms or a branched or cyclic alkylene, alkylidene, alkyleneoxy or thioalkyleneoxy group having 3 to 40 C atoms or an alkenylene or alkynylene group having 2 to 40 C atoms, each of which may be substituted by one or more radicals R 2 , where one or more 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 , S═O, SO 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 a di-, tri-, tetra-, penta- or hexavalent aromatic or heteroaromatic ring system having 5 to 80 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , or P(R 2 ) 3-p , P(═O)(R 2 ) 3-p , C(R 2 ) 4-p , Si(R 2 ) 4-p , N(Ar) 3-p , or a combination of two, three, four or five of these systems; or L is a chemical bond;

n is on each occurrence, identically or differently, 0 or 1; and

p is 2, 3, 4, 5 or 6, with the proviso that p is not greater than the maximum valence of L.

2. The compound according to claim 1 , wherein the compounds of the formulae (2) and (3) are compounds of the above-mentioned formulae (11d) to (31e) in which in each case two or more of these units, which is optionally identical or different, are bridged to one another by a divalent or polyvalent group L, which is in each case bonded instead of a substituent R in the para-position to X;

or in that the compounds of the formula (4) are compounds of the above-mentioned formulae (11d) to (31e) in which in each case two of these units, which is optionally identical or different, are bridged to one another by a spiro carbon atom, which is present instead of the group Y.

3. The compound according to claim 1 , wherein

R 1 are on each occurrence, identically or differently, H, D, F, Cl, Br, I, CN, NO 2 , N(Ar) 2 , N(R 2 ) 2 , C(═O)Ar, C(═O)R 1 , P(═O)(Ar) 2 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, each of which is optionally substituted by one or more radicals R 2 , where one or more 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 , 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 , an aryloxy or heteroaryloxy 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 , where two or more adjacent substituents R or two substituents R 1 which are bonded in the same group Y may optionally form a mono- or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which is optionally substituted by one or more radicals R 2 , with one another;

L is a di-, tri-, tetra-, penta- or hexavalent straight-chain alkylene, alkylidene, alkyleneoxy or thioalkyleneoxy group having 1 to 40 C atoms or a branched or cyclic alkylene, alkylidene, alkyleneoxy or thioalkyleneoxy group having 3 to 40 C atoms or an alkenylene or alkynylene group having 2 to 40 C atoms, each of which may be substituted by one or more radicals R 2 , where one or more 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 , S═O, SO 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 a di-, tri-, tetra-, penta- or hexavalent aromatic or heteroaromatic ring system having 5 to 40, aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , or P(R 2 ) 3-p , P(═O)(R 2 ) 3-p , C(R 2 ) 4-p , Si(R) 4-p , N(Ar) 3-p , or a combination of two, three, four or five of these systems; or L is a chemical bond and

X is N.

4. The compound according to claim 1 , wherein X stands on each occurrence, identically or differently, for N or P.

5. The compound according to claim 1 , wherein at least one substituent R, R 1 and/or R 2 is selected from structures of the following formulae (32) to (35):

and/or in that at least one group L is selected from structures of the following formulae (36) to (38):

where R 2 has the meaning given in claim 1 , * indicates the position of the bond from the group of the formulae (32) to (38).

6. The compound according to claim 1 , wherein at least substituent R, is selected from structures of the following formulae (32) to (35):

and/or in that at least one group L is selected from structures of the following formulae (36) to (38):

7. A process for the preparation of the compound according to claim 1 , comprising the reaction steps of:

a) synthesis of the skeleton which is only bridged by one group Y;

b) introducing the second and optionally third group Y, by an intramolecular ring-closure reaction;

c) introducing the radical(s) R.

8. An oligomer, polymer or dendrimer comprising one or more compounds according to claim 1 , where one or more bonds to the polymer, oligomer or dendrimer are present instead of one or more radicals R, R 1 and/or R 2 .

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

10. An electronic device which comprises an oligomer, polymer or dendrimer according to claim 6 .

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

12. An organic electroluminescent device which comprises an oligomer, polymer or dendrimer according to claim 6 .

13. The electronic device as claimed in claim 9 , wherein the device is an organic electroluminescent device (OLED, PLED), an organic integrated circuit (O-IC), an organic field-effect transistor (O-FET), an organic thin-film transistor (O-TFT), an organic light-emitting transistor (O-LET), an organic solar cell (O-SC), an organic optical detector, an organic photoreceptor, an organic field-quench device (O-FQD), a light-emitting electrochemical cell (LEC), an organic laser diode (O-laser) or an organic plasmon emitting device.

14. An organic electroluminescent device which comprises the compound according to claim 1 as matrix material for fluorescent or phosphorescent emitters, in particular for phosphorescent emitters, in an emitting layer and/or as hole-blocking material in a hole-blocking layer and/or as electron-transport material in an electron-transport layer and/or as electron- or exciton-blocking material in an electron-blocking or exciton-blocking layer and/or as hole-transport material in a hole-transport or hole-injection layer.