Materials for organic electroluminescent devices

1. A compound of the formula (1)

where the following applies to the symbols used:

Ar is selected from phenyl, 2- phenanthrenyl, 3- phenanthrenyl, 9-phenanthrenyl, para-phenylene-1-naphthyl, para-phenylene-2-naphthyl, 2-fluorenyl or 2-spirobifluorenyl, which is optionally substituted by one or more radicals R1, or the Ar group is selected from the formulae (8), (9), (10) and (11):

Ar2 is an aryl or heteroaryl group having 5 to 16 aromatic ring atoms which is optionally substituted by one or more radicals R1;

q is 1;

R1 is, identically or differently on each occurrence, H, D, F, Cl, Br, I, CHO, N(Ar1) 2 , C(═O)Ar1, P(Ar1) 2 , P(═O)(Ar1) 2 , S(═O)Ar1, S(═O) 2 Ar1, CR3=CR3Ar1, CN, NO 2 , Si(R3) 3 , B(OAr1) 2 , B(OR3) 2 , OSO 2 R3, OH, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, which is optionally substituted by one or more radicals R3, where one or more non-adjacent CH 2 groups is optionally replaced by R3C═CR3, C≡C, Si(R3) 2 , Ge(R3) 2 , Sn(R3) 2 , C═O, C═S, C═Se, C═NR3, P(═O)(R3), SO, SO 2 , NR3, O, S or CONR3 and where one or more H atoms is optionally replaced by F, Cl, Br, I, CN or NO 2 , or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which are each optionally substituted by one or more non-aromatic radicals R1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more non-aromatic radicals R1;

R2 is, identically or differently on each occurrence, R1;

Ar1 is, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more non-aromatic radicals R3; two radicals Ar1 which are bonded to the same nitrogen or phosphorus atom may optionally be linked to one another by a single bond or a bridge selected from B(R3), C(R3) 2 , Si(R3) 2 , C═O, C═NR3, C═C(R3) 2 , O, S, S═O, SO 2 , N(R3), P(R3) and P(═O)R3;

R3 is on each occurrence, identically or differently, H or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, in which, in addition, one or more H atoms is optionally replaced by F;

with the provisos that R2 in positions 2, 3, 6, and 7 of anthracene is not N(Ar1) 2 or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and Ar is not ortho-biphenyl, meta-biphenyl, or para-biphenyl.

2. The compound according to claim 1 , wherein the symbols R1 and R2, identically or differently on each occurrence, stand for H, F, N(Ar1) 2 , C(═O)Ar1, P(Ar1) 2 , P(═O)(Ar1) 2 , S(═O)Ar1, S(═O) 2 Ar1, CR3=CR3Ar1, Si(R3) 3 , B(OAr1) 2 , B(OR3) 2 , a straight-chain alkyl or alkoxy group having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, which is optionally substituted by one or more radicals R3, where one or more non-adjacent CH 2 groups is optionally replaced by R3C═CR3, C≡C, Si(R3) 2 , C═O, P(═O)(R3), SO, SO 2 , NR3, O or S and where one or more H atoms is optionally replaced by F, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which are each optionally substituted by one or more non-aromatic radicals R1.

3. A process for the preparation of the compound according to claim 1 , which comprises substituting 9-aryl-substituted anthracene in the 10-position by a reactive leaving group, and coupling the 9-aryl-substituted anthracene to a phenanthrene derivative which is functionalised in the 3-position, where both the phenanthrene and also the anthracene, benzanthracene or tetracene are optionally substituted by one or more substituents R1.

4. The process as claimed in claim 3 , wherein the reactive leaving group is chlorine, bromine, iodine, triflate, tosylate, boronic acid or boronic acid ester, or a corresponding benz[a]anthracene or tetracene.

5. An electronic device which comprises at least one compound according to claim 1 .

6. The electronic device according to claim 5 , wherein the device is selected from the group consisting of an organic electroluminescent device (OLED), organic field-effect transistor (O-FET), organic thin-film transistor (O-TFT), organic light-emitting transistor (O-LET), organic integrated circuit (O-IC), organic solar cell (O-SC), organic field-quench device (O-FQD), light-emitting electrochemical cell (LEC), organic laser diode (O-laser) and organic photoreceptor.

7. An organic electroluminescent device comprising anode, cathode and at least one emitting layer, wherein at least one organic layer, which may be an emitting layer or another layer, comprises at least one compound according to claim 1 .

8. The organic electroluminescent device according to claim 7 , wherein the compound of formula (1) is employed as a host material for fluorescent dopants.

9. The organic electroluminescent device according to claim 8 , wherein the fluorescent dopants comprise compounds which are selected from the group consisting of monostyrylamine, distyrylamine, tristyrylamine, tetrastyrylamine, styrylphosphine, styryl ether, arylamine, indenofluorenamine, indenofluorenediamine, benzoindenofluorenamine, benzoindenofluorenediamine, dibenzoindenfluorenamine and dibenzoindenfluorenediamine.

10. The organic electroluminescent device according to claim 9 , wherein the compound of the formula (1) is employed as electron-transport material or as hole-blocking material in a fluorescent or phosphorescent device.

11. A compound selected from the group consisting of

12. The compound according to claim 11 , wherein the compound is of the formula (1) or (3).

13. The compound according to claim 1 , wherein the compound of the formula (1) is a compound of the formula (2):

14. The compound according to claim 1 , wherein formula (1) is:

wherein

R2a, R2d, R2e, and R2h are, identically or differently on each occurrence, H, D, F, Cl, Br, I, CHO, N(Ar1) 2 , C(═O)Ar1, P(Ar1) 2 , P(═O)(Ar1) 2 , S(═O)Ar1, S(═O) 2 Ar1, CR3=CR3Ar1, CN, NO 2 , Si(R3) 3 , B(OAr1) 2 , B(OR3) 2 , OSO 2 R3, OH, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, which is optionally substituted by one or more radicals R3, where one or more non-adjacent CH 2 groups is optionally replaced by R3C═CR3, C≡C, Si(R3) 2 , Ge(R3) 2 , Sn(R3) 2 , C═O, C═S, C═Se, C═NR3, P(═O)(R3), SO, SO 2 , NR3, O, S or CONR3 and where one or more H atoms is optionally replaced by F, Cl, Br, I, CN or NO 2 , or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which are each optionally substituted by one or more non-aromatic radicals R1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more non-aromatic radicals R1; and

R2b, R2c, R2f, and R2g are, identically or differently on each occurrence, H, D, F, Cl, Br, I, CHO, C(═O)Ar1, P(Ar1) 2 , P(═O)(Ar1) 2 , S(═O)Ar1, S(═O) 2 Ar1, CR3=CR3Ar1, CN, NO 2 , Si(R3) 3 , B(OAr1) 2 , B(OR3) 2 , OSO 2 R3, OH, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, which is optionally substituted by one or more radicals R3, where one or more non-adjacent CH 2 groups is optionally replaced by R3C═CR3, C≡C, Si(R3) 2 , Ge(R3) 2 , Sn(R3) 2 , C═O, C═S, C═Se, C═NR3, P(═O)(R3), SO, SO 2 , NR3, O, S or CONR3 and where one or more H atoms is optionally replaced by F, Cl, Br, I, CN or NO 2 .

15. The compound according to claim 1 , wherein R2 is identically or differently on each occurrence, H, D, F, Cl, Br, I, CHO, C(═O)Ar1, P(Ar1) 2 , P(═O)(Ar1) 2 , S(═O)Ar1, S(═O) 2 Ar1, CR3=CR3Ar1, CN, NO 2 , Si(R3) 3 , B(OAr1) 2 , B(OR3) 2 , OSO 2 R3, OH, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, which is optionally substituted by one or more radicals R3, where one or more non-adjacent CH 2 groups is optionally replaced by R3C═CR3, C≡C, Si(R3) 2 , Ge(R3) 2 , Sn(R3) 2 , C═O, C═S, C═Se, C═NR3, P(═O)(R3), SO, SO 2 , NR3, O, S or CONR3 and where one or more H atoms is optionally replaced by F, Cl, Br, I, CN or NO 2 .

16. A compound of the formula (1)

where the following applies to the symbols used:

Ar is selected from phenyl which is optionally substituted by one or more radicals R1, or the Ar group is selected from the formulae (8), (9), (10) and (11):

Ar2 is phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, chrysenyl, 1-pyrenyl, 2-pyrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 9-phenanthrenyl, 2-benzimidazole or fluoranthenyl, which is optionally substituted by one or more radicals R1;

q is 1;

R1 is, identically or differently on each occurrence, H, D, F, Cl, Br, I, CHO, N(Ar1) 2 , C(═O)Ar1, P(Ar1) 2 , P(═O)(Ar1) 2 , S(═O)Ar1, S(═O) 2 Ar1, CR3=CR3Ar1, CN, NO 2 , Si(R3) 3 , B(OAr1) 2 , B(OR3) 2 , OSO 2 R3, OH, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, which is optionally substituted by one or more radicals R3, where one or more non-adjacent CH 2 groups is optionally replaced by R3C═CR3, C≡C, Si(R3) 2 , Ge(R3) 2 , Sn(R3) 2 , C═O, C═S, C═Se, C═NR3, P(═O)(R3), SO, SO 2 , NR3, O, S or CONR3 and where one or more H atoms is optionally replaced by F, Cl, Br, I, CN or NO 2 , or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which are each optionally substituted by one or more non-aromatic radicals R1, or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more non-aromatic radicals R1;

R2 is, identically or differently on each occurrence, R1;

Ar1 is, identically or differently on each occurrence, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more non-aromatic radicals R3; two radicals Ar1 which are bonded to the same nitrogen or phosphorus atom may optionally be linked to one another by a single bond or a bridge selected from B(R3), C(R3) 2 , Si(R3) 2 , C═O, C═NR3, C═C(R3) 2 , O, S, S═O, SO 2 , N(R3), P(R3) and P(═O)R3;

R3 is on each occurrence, identically or differently, H or an aliphatic, aromatic and/or heteroaromatic hydrocarbon radical having 1 to 20 C atoms, in which, in addition, one or more H atoms is optionally replaced by F;

with the provisos that R2 in positions 2, 3, 6, and 7 of anthracene is not N(Ar1) 2 or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and Ar is not ortho-biphenyl, meta-biphenyl, or para-biphenyl.

17. The compound according to claim 1 , wherein Ar2 is phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, chrysenyl, 1-pyrenyl, 2-pyrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 9-phenanthrenyl, 2-benzimidazole or fluoranthenyl, which is optionally substituted by one or more radicals R1.