Phenanthrene compounds for organic electronic devices

1. A compound of the general formula (1)

where the following applies to the symbols and indices occurring:

X is on each occurrence, identically or differently, N and CR 1 , where a maximum of 2 of the X is optionally equal to N;

L is a single bond or a divalent aryl or heteroaryl group having 12 to 40 ring atoms, which is optionally substituted by one or more radicals R 2 , where, if L is a single bond, the nitrogen is bonded directly to position 3 of the phenanthrene;

Ar 1 is selected from formulae (37)-(57):

Ar 2 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, where the ring or ring system is optionally substituted by one or more radicals R 4 , where, if both Ar 1 and also Ar 2 are phenyl radicals, at least one R 4 on the phenyl radicals is not equal to H and this at least one radical R 4 optionally contains one or more aromatic or heteroaromatic rings;

R 1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(═O)R 2 , CN, Si(R 2 ) 3 , NO 2 , P(═O)(R 2 ) 2 , S(═O)R 2 , S(═O) 2 R 2 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R 2 and where one or more CH 2 groups in the above-mentioned groups is optionally replaced by —R 2 C═CR 2 —, —C≡C—, Si(R 2 ) 2 , C═O, C═S, C≡NR 2 , —C(O)O—, —C(═O)NR 2 —, P(═O)(R 2 ), —O—, —S—, SO or SO 2 and where one or more H atoms in the above-mentioned groups is optionally replaced by D, F, Cl, Br, I, CN or NO 2 , or an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2 , where two or more radicals R 1 is optionally linked to one another and may form a ring;

R 4 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(═O)R 2 , CN, Si(R 2 ) 3 , NR 2 , NO 2 , P(═O)(R 2 ) 2 , S(═O)R 2 , S(═O) 2 R 2 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R 2 and where one or more CH 2 groups in the above-mentioned groups is optionally replaced by —R 2 C═CR 2 —, Si(R 2 ) 2 , C═O, C═S, C═NR 2 , —C(═O)O—, —C(═O)NR 2 —, P(═O)(R 2 ), —O—, —S—, SO or SO 2 and where one or more H atoms in the above-mentioned groups is optionally replaced by D, F, Cl, Br, CN or NO 2 , or an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R 2 , where two or more radicals R 4 is optionally linked to one another and may form a ring;

R 2 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, C(═O)R 3 , CN, Si(R 3 ) 3 , NO 2 , P(═O)(R 3 ) 2 , S(═O)R 3 , S(═O) 2 R 3 , a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where the above-mentioned groups may each be substituted by one or more radicals R 3 and where one or more CH 2 groups in the above-mentioned groups is optionally replaced by —R 3 C═CR 3 —, Si(R 3 ) 2 , CO, C═S, C═NR 3 , —C(═O)O—, —C(═O)NR 3 —, P(═O)(R 3 ), —O—, —S—, SO or SO 2 and where one or more H atoms in the above-mentioned groups is optionally replaced by D, F, Cl, Br, I, CN or NO 2 , or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R 3 , or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R 3 , where two or more radicals R 2 is optionally linked to one another and optionally form a ring;

R 3 is on each occurrence, identically or differently, H, D, F or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms is optionally replaced by D or F; two or more substituents R 3 here is optionally linked to one another and optionally form a ring;

where the compound of the formula (1), besides the phenanthrene, contains no further condensed aromatic or heteroaromatic ring having more than 10 ring atoms and

where the radicals R 1 on the phenanthrene in formula (1) contain no further amine groups.

2. The compound according to claim 1 , wherein the compound is of the general formula

where the definitions from claim 1 apply to the symbols used.

3. The compound according to claim 1 , wherein L is an aromatic ring system selected from the group consisting of biphenylenes, terphenylenes and the compounds of the formula (101a) and (101b),

where Y is equal to C(R 2 ) 2 , NR 2 , O, Si(R 2 ) 2 or S.

4. The compound according to claim 3 , wherein Y is C(R 2 ) 2 or NR 2 .

5. The compound according to claim 1 , wherein L is a single bond, so that the amine group is bonded directly to the phenanthrene.

6. The compound according to claim 1 , wherein the compound contains in total at least 26 ring atoms.

7. The compound according to claim 1 , wherein the compound contains only one amine group.

8. A process for the preparation of the compound according to claim 1 which comprises a one-step Buchwald coupling by reaction of a phenanthrene derivative which contains a leaving group with Ar 2 —NH—Ar 1 .

9. A process for the preparation of the compound according to claim 1 which comprises a two-step Buchwald coupling by stepwise reaction of a phenanthrene derivative which contains a leaving group with (1) Ar 2 —NH 2 and (2) NH 2 —Ar 1 .

10. An oligomer, polymer or dendrimer containing one or more claim 1 compounds according to claim 1 , where the bond(s) to the polymer, oligomer or dendrimer is optionally localised at any desired positions in formula (1) which are substituted by R 1 , R 4 or R 2 .

11. A composition comprising one or more compound according to claim 1 and at least one further organically functional material selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron-transport materials, electron-injection materials, hole-conductor materials, hole-injection materials, electron-blocking materials and hole-blocking materials.

12. A formulation comprising at least one compound according to claim 1 and at least one solvent.

13. An electronic device comprising at least one compound according to claim 1 .

14. The electronic device according to claim 13 , wherein the device is selected from organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field-quench devices (O-FQDs), light-emitting electrochemical cells (LECs), organic laser diodes (O-lasers) and organic electroluminescent devices (OLEDs).

15. An electronic device which is selected from the group of organic electroluminescent devices, which comprises the compound according to claim 1 employed in one or more of the following functions:

as hole-transport material in a hole-transport or hole-injection layer,

as matrix material in an emitting layer,

as electron-blocking material,

as exciton-blocking material.

16. The compound according to claim 1 , wherein the compound is of the formula

wherein L, Ar 1 , Ar 2 , and R 1 are defined in claim 1 .

17. The compound according to claim 1 , wherein the compound is of the formula

wherein L, Ar 1 and Ar 2 are defined in claim 1 .