Bridged triarylamines and -phosphines as materials for electronic devices

1. A compound of formulae (I-1) to (I-4)

wherein

X is N, P, or P═O;

Y is, identically or differently on each occurrence, C(R 1 ) 2 , C═O, C═NR 1 , O, S, SO, SO 2 , PR 1 , POR 1 , NAr, NR 1 , or a single bond;

Z is identically or differently on each occurrence, CR 2 , N, or C if a group Y or T is bonded to Z;

T is, identically or differently on each occurrence, C(R 1 ) 2 , C═O, C═NR 1 , O, S, SO, SO 2 , PR 1 , POR 1 , NAr, NR 1 , or a single bond;

A is Ar 3 , which is an aryl group with 6 to 14 aromatic ring carbons, optionally substituted by one or more radicals R 2 , wherein the bond to a group T starts from the aromatic ring of the group Ar 3 ;

Ar are, identically or differently on each occurrence, an aryl or heteroaryl group having 5 to 30 aromatic ring atoms optionally substituted by one or more radicals R 2 ;

R 1 and R 2 are, identically or differently on each occurrence, H, D, F, Cl, Br, I, CHO, NAr 2 , N(R 3 ) 2 , C(═O)R 3 , P(═O)(R 3 ) 2 , S(═O)R 3 , CR 3 ═C(R 3 ) 2 , CN, NO 2 , Si(R 3 ) 3 , B(OR 3 ) 2 , OSO 2 R 3 , OH, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms, 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 , wherein one or more non-adjacent CH 2 groups are 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—, —COO—, or —CONR 3 —, and wherein one or more H atoms are optionally replaced by D, F, Cl, Br, I, CN, NO 2 , an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which in each case is optionally substituted by one or more radicals R 3 , an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, optionally substituted by one or more radicals R 3 , or a combination of these systems, wherein two or more radicals R 1 and R 2 optionally define a ring or ring system;

R 3 is, identically or differently on each occurrence, H, D, F, Cl, Br, I, CHO, NAr 2 , N(R 4 ) 2 , C(═O)R 4 , P(═O)(R 4 ) 2 , S(═O)R 4 , S(═O) 2 R 4 , CR 4 ═C(R 4 ) 2 , CN, NO 2 , Si(R 4 ) 3 , B(OR 4 ) 2 , OSO 2 R 4 , OH, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms, 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 4 ,

wherein one or more non-adjacent CH 2 groups are optionally replaced by —R 4 C═CR 4 —, —C═C—, Si(R 4 ) 2 , Ge(R 4 ) 2 , Sn(R 4 ) 2 , C═O, C═S, C═Se, C═NR 4 , P(═O)(R 4 ), SO, SO 2 , NR 4 , —O—, —S—, —COO—, or —CONR 4 —, and wherein one or more H atoms are 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, optionally substituted by one or more radicals R 4 , an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, optionally substituted by one or more radicals R 4 , or a combination of these systems, wherein two or more radicals R 3 optionally define a ring or ring system;

R 4 is, identically or differently on each occurrence, H, D, F, or an aliphatic, aromatic and/or heteroaromatic organic radical having 1 to 20 C atoms, wherein one or more H atoms are optionally replaced by F, and wherein two or more identical or different substituents R 4 optionally define a ring or ring system;

n is, on each occurrence, independently of one another, 0 or 1, with the proviso that the sum of all values for n is greater than or equal to 1;

m is, on each occurrence, independently of one another, 0 or 1, with the proviso that the sum of all values for m is greater than or equal to 1;

and with the proviso that at least one group Y is a single bond.

2. The compound of claim 1 , wherein X is N.

3. The compound of claim 1 , wherein Y is, identically or differently on each occurrence, C(R 1 ) 2 , S, O, C═O, NR 1 , or a single bond, with the proviso that at least one group Y is a single bond.

4. The compound of claim 1 , wherein the sum of the values of n and m is 2 or 3.

5. The compound of claim 1 , of formula I-1.

6. The compound of claim 1 , wherein said compound is of formulae (I5) to (I-10)

wherein

Z is, identically or differently on each occurrence, CR 2 or N if no group Y or T is bonded to the group Z, or is on each occurrence C if a group Y or T is bonded to the group Z.

7. An oligomer, polymer, or dendrimer comprising one or more compounds of claim 1 , wherein one or more bonds to said oligomer, polymer or dendrimer replace one or more bonds to one or more substituents.

8. A formulation comprising at least one compound of claim 1 and at least one solvent.

9. A process for preparing the compound of claim 1 , comprising

a) synthesizing a precursor molecule unbridged in the relevant position and carrying a group Y* and/or T*; and

b) performing the ring-closure reaction, introducing the bridge Y and/or T.

10. An electronic device comprising the compound of claim 1 .

11. The electronic device of claim 10 , wherein said compound is employed as matrix material in an emitting layer, optionally comprising one or more phosphorescent emitters, and/or is employed as hole-transport material in a hole-transport layer and/or in a hole-injection layer, and/or is employed as emitting material in an emitting layer.

12. A formulation comprising at least one oligomer, polymer, or dendrimer of claim 7 and at least one solvent.

13. An electronic device comprising the oligomer, polymer, or dendrimer of claim 7 .

14. The electronic device of claim 10 , wherein said electronic device is an organic integrated circuit, organic field-effect transistor, organic thin-film transistor, organic light-emitting transistor, organic solar cell, organic optical detector, organic photoreceptor, organic field-quench device, light-emitting electrochemical cell, organic laser diode, or organic electroluminescent device.

15. The electronic device of claim 13 , wherein said electronic device is an organic integrated circuit, organic field-effect transistor, organic thin-film transistor, organic light-emitting transistor, organic solar cell, organic optical detector, organic photoreceptor, organic field-quench device, light-emitting electrochemical cell, organic laser diode, or organic electroluminescent device.

16. The compound of claim 1 of formula I-2.

17. The compound of claim 16 , wherein X is N; Y is, identically or differently on each occurrence, C(R 1 ) 2 , S, O, C═O, NR 1 , or a single bond, with the proviso that at least one group Y is a single bond; and the sum of the values of n and m is 2 or 3.

18. The compound of claim 1 of formula I-3.

19. The compound of claim 18 , wherein X is N; Y is, identically or differently on each occurrence, C(R 1 ) 2 , S, O, C═O, NR 1 , or a single bond, with the proviso that at least one group Y is a single bond; and the sum of the values of n and m is 2 or 3.

20. The compound of claim 1 of formula I-4.

21. The compound of claim 20 , wherein X is N; Y is, identically or differently on each occurrence, C(R 1 ) 2 , S, O, C═O, NR 1 , or a single bond, with the proviso that at least one group Y is a single bond; and the sum of the values of n and m is 2 or 3.

22. The compound of claim 5 , wherein X is N; Y is, identically or differently on each occurrence, C(R 1 ) 2 , S, O, C═O, NR 1 , or a single bond, with the proviso that at least one group Y is a single bond; and the sum of the values of n and m is 2 or 3.

23. The compound of claim 1 , wherein T is, identically or differently on each occurrence, C(R 1 ) 2 .

24. The compound of claim 1 , wherein Y is, identically or differently on each occurrence, C(R 1 ) 2 or a single bond, with the proviso that at least one group Y is a single bond.

25. The compound of claim 1 , wherein T is, identically or differently on each occurrence, C(R 1 ) 2 ; and Y is, identically or differently on each occurrence, C(R 1 ) 2 or a single bond, with the proviso that at least one group Y is a single bond.

26. The compound of claim 1 , wherein Z is, identically or differently on each occurrence, CR 2 , or if a group Y or T is bonded to the group Z, then Z is C.