Materials for organic electroluminescent devices

1. A compound of the formula (4), (5), (7), (8), and (19-(22)

where the following applies to the symbols and indices used:

X is on each occurrence, identically or differently, CR; or X stands for C if a group L is bonded to this group X;

Y, Y 1 , Y 2 and Y 3 is on each occurrence, identically or differently, C(R 1 ) 2 ;

Z is on each occurrence, identically or differently, CR or N; or Z stands for C if a group Y 1 or Y 2 or Y 3 is bonded to this group Z;

a group R is replaced by L in the formula (7) and (8) if the group L is bonded in the corresponding carbon atom,

L is, identically or differently, R if q=1 or 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, which may be substituted by in each case one or more radicals R 2 , where in each case one or more non-adjacent CH 2 groups may be replaced by —R 2 C═CR 2 —, —C≡C, Si(R 2 ) 2 , C═O, C═NR 2 , P(═O)R 2 , S═O, SO 2 , —O—, —S— or —CONR 2 — and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 , or a di-, tri-, tetra-, penta- or hexavalent aromatic ring system having 5 to 40, aromatic ring atoms, which may be substituted by one or more radicals R 2 , or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which contains, as heteroaryl groups, exclusively sulfur-containing or oxygen-containing heteroaryl groups and which may be substituted by one or more radicals R 2 , or P(R 2 ) 3-r , P(═O)(R 2 ) 3-r , C(R 2 ) 4-r , Si(R 2 ) 4-r , N(Ar) 3-r , where r stands for 2, 3 or 4, with the proviso that r is not greater than the maximum valence of L; or L is a chemical bond, in which case q=2; the valence of the group L=q+1 here;

q is 1, 2, 3, 4, 5 or 6;

R and R 1 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO 2 , C(═O)Ar, C(═O)R 2 , 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 may be substituted by one or more radicals R 2 , where one or more non-adjacent CH 2 groups may be replaced by R 2 C═CR 2 , Si(R 2 ) 2 , C═0, C═NR 2 , P(═O)(R 2 ), SO, SO 2 , NR 2 , O, S or CONR 2 and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 , an aromatic ring system having 6 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2 , a heteroaromatic ring system having 5 to 60 aromatic ring atoms, which contains, as heteroaryl groups, sulfur-containing or oxygen-containing heteroaryl groups and which may be substituted by one or more radicals R 2 , an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 2 , or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 2 , where 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 with one another, which may be substituted by one or more radicals R 2 ; furthermore, two adjacent radicals R may form a condensed-on benzo ring, which may be substituted by one or more radicals R 2 ;

R 2 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO 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 may be substituted by one or more radicals R 3 , where one or more non-adjacent CH 2 groups may be replaced by R 3 C═CR 3 , C≡C, Si(R 3 ) 2 , C═O, C═NR 3 , P(═O)(R 3 ), SO, SO 2 , NR 3 , O, S or CONR 3 and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 , an aromatic 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 may be substituted by one or more radicals R 3 , or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms;

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

R 3 is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aromatic ring system having 5 to 30 aromatic ring atoms, in which one or more H atoms may be replaced by D, F, Cl, Br, I or CN

the following compound is excluded from the invention:

2. The compound according to claim 1 , wherein the compound is a compound of the formula (4a) or (5a),

where the symbols and indices used have the meanings given in claim 1 .

3. The compound according to claim 1 , wherein the compound is a compound of the formulae (19a) to (22a), (24) or (25),

where the symbols used have the meanings given under claim 1 .

4. The compound according to claim 1 , wherein the compound is a compound of the formulae (19b) to (22b), (24a) or (25a),

where the symbols used have the meanings given in claim 1 .

5. The compound according to claim 1 , wherein R, if R stands for an aromatic or heteroaromatic ring system, is selected from the groups of the formulae (26) to (58),

where the dashed bond indicates the bonding to the basic structure and the groups may be substituted by one or more radicals R 2 .

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

a) synthesis of the corresponding basic structure which does not yet contain a bridge Y; and

b) introducing the group Y.

7. A mixture comprising at least one compound according to claim 1 and at least one further compound.

8. A formulation comprising at least one compound according to claim 1 and one or more solvents.

9. The formulation as claimed in claim 8 , wherein the formulation is a solution, a suspension or a miniemulsion.

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

11. The electronic device as claimed in claim 10 , wherein the device is selected from the group consisting of organic electroluminescent devices, organic integrated circuits, organic field-effect transistors, organic thin-film transistors, organic light-emitting transistors, organic solar cells, organic dye-sensitised solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and “organic plasmon emitting devices”.

12. An organic electroluminescent device comprising the compound according to claim 1 is employed as matrix material for fluorescent or phosphorescent emitters and/or in an electron-blocking or exciton-blocking layer and/or in a hole-transport or hole-injection layer.