Materials for organic electroluminescent devices
The present invention relates to compounds which are suitable for use in electronic devices, and to electronic devices, in particular organic electroluminescent devices, comprising these compounds.
1. A compound of the formula (1) or formula (1A),
where the following applies to the symbols and indices used:
Y is on each occurrence, identically or differently, CR 1 or N, with the proviso that at least one group Y stands for N;
X is on each occurrence, identically or differently, CR 1 or N; or two adjacent X stand for S, O or NR 1 , so that a five-membered ring forms; or two adjacent X stand for a group of the following formula (2), (3) or (4),
where ^ indicates the corresponding adjacent groups X in the formula (1);
V is on each occurrence, identically or differently, C(R 1 ) 2 , NR 1 , O, S, BR 1 , Si(R 1 ) 2 or C═O;
Z is on each occurrence, identically or differently, CR 1 or N;
Ar is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R 1 ;
R is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CN, N(Ar 1 ) 2 , a straight-chain alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl group having 3 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 or O and where one or more H atoms is optionally replaced by D or F, or an aromatic ring system having 6 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 ; wherein the aromatic ring system is selected from benzene, ortho-, meta-para-biphenyl, ortho-, meta-, para- or branched terphenyl, ortho-, meta-, para- or branched quaterphenyl, 1-, 2- or 3-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, 1- or 2-naphthyl, phenanthrene, or combinations of two or three of these groups, each of which may be substituted by one or more radicals R 1 ; two adjacent substituents R here may form a monocyclic or polycyclic, aliphatic or aromatic ring system, which is optionally substituted by one or more radicals R 2 ;
R 1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CN, NO 2 , N(Ar 1 ) 2 , N(R 2 ) 2 , C(═O)Ar 1 , C(═O)R 2 , P(═O)(Ar 1 ) 2 , P(Ar 1 ) 2 , B(Ar 1 ) 2 , Si(Ar 1 ) 3 , Si(R 2 ) 3 , 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 , C═O, C═S, 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 ; two adjacent substituents R 1 here may optionally form a monocyclic or polycyclic, or aliphatic ring system, which is optionally substituted by one or more radicals R 2 ;
Ar 1 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 2 ; two radicals Ar 1 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 2 ), C(R 2 ) 2 , O or S;
R 2 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms, or 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 2 may form a mono- or polycyclic, aliphatic ring system with one another;
m and n are on each occurrence, identically or differently, 0 or 1, with the proviso that m+n≥1;
p is on each occurrence, identically or differently, 0, 1, 2, 3 or 4;
q is 0, 1 or 2.
2. The compound according to claim 1 , wherein the X stands, identically or differently on each occurrence, for the CR 1 or the N, where a maximum of one group X per ring stands for the N; or the two adjacent groups X stand for a group of the formula (2) or (3), where the Z stands, identically or differently on each occurrence, for the CR 1 and the V stands, identically or differently on each occurrence, for the NR 1 , the C(R 1 ) 2 , the O or the S.
3. The compound according to claim 1 , wherein the compound is selected from the compounds of the formulae (5) to (12),
where the symbols and indices used have the meanings given in claim 1 , and the V stands for the NR 1 , the C(R 1 ) 2 , the O or the S.
4. The compound according to claim 1 , wherein the compound is selected from the structures of the formulae (5a) to (12a),
where the symbols and indices used have the meanings given in claim 1 .
5. The compound according to claim 1 , wherein the R is selected, identically or differently on each occurrence, from the group consisting of H, F, CN, N(Ar 1 ) 2 , a straight-chain alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic ring system having 6 to 30 aromatic ring atoms, where the aromatic ring system does not contain heteroaryl groups, which is optionally substituted by one or more non-aromatic radicals R 2 , and wherein the aromatic ring system is selected from benzene, ortho-, meta-para-biphenyl, ortho-, meta-, para- or branched terphenyl, ortho-, meta-, para- or branched quaterphenyl, 1-, 2- or 3-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, 1- or 2-naphthyl, phenanthrene, or combinations of two or three of these groups, each of which may be substituted by one or more radicals R 1 and in that the R 1 is selected, identically or differently on each occurrence, from the group consisting of H, D, F, Br, CN, N(Ar 1 ) 2 , C(═O)Ar 1 , P(═O)(Ar 1 ) 2 , a straight-chain alkyl or alkoxy group having 1 to 10 C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms or an alkenyl or alkynyl group having 2 to 10 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 O and where one or more H atoms is optionally replaced by D or F, 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 2 .
6. The compound according to claim 1 , wherein the Ar is selected from aromatic or heteroaromatic ring systems having 5 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R 1 , each of which is optionally substituted by one or more radicals R 1 .
7. The compound according to claim 1 , wherein the Ar is benzene, ortho-, meta- or para-biphenyl, ortho-, meta-, para- or branched terphenyl, ortho-, meta-, para- or branched quaterphenyl, 1-, 2- or 3-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, 1- or 2-naphthyl, pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, 1-, 2- or 3-carbazole, 1-, 2- or 3-dibenzofuran, 1-, 2- or 3-dibenzothiophene, indenocarbazole, indolocarbazole, 2-, 3- or 4-pyridine, 2-, 4- or 5-pyrimidine, pyrazine, pyridazine, triazine, anthracene, phenanthrene, triphenylene, pyrene, benzanthracene, or combinations of two or three of these groups, each of which is optionally substituted by one or more radicals R 1 .
8. The compound according to claim 1 , wherein, in the group of the following formula (Het-Ar),
which is present in the compound according to claim 1 for n=1 and which is bonded to the Ar or, for m=0, to the nitrogen, at least one group Y and a maximum of three groups Y stand for N and the other groups Y stand for CR 1 .
9. The compound according to claim 8 , wherein the group (Het-Ar) is selected from the groups of the formulae (Het-Ar-1) to (Het-Ar-10),
wherein the dashed bond represents the bond to the Ar or, for m=0, the bond to the nitrogen, and
R 1 is on each occurrence, identically or differently, H, D, F, Cl, Br, I, CN, NO 2 , N(Ar 1 ) 2 , N(R 2 ) 2 , C(═O)Ar 1 , C(═O)R 2 , P(═O)(Ar 1 ) 2 , P(Ar 1 ) 2 , B(Ar 1 ) 2 , Si(Ar 1 ) 3 , Si(R 2 ) 3 , 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 , C═O, C═S, 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 ; two adjacent substituents R 1 here may optionally form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which is optionally substituted by one or more radicals R 2 ;
Ar 1 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 2 ; two radicals Ar 1 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 2 ), C(R 2 ) 2 , O or S;
R 2 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20 C atoms, or 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 2 may form a mono- or polycyclic, aliphatic ring system with one another.
10. The compound according to claim 1 , wherein the compound contains no condensed aryl or heteroaryl groups in which more than two six-membered rings are condensed directly onto one another.
11. A process for the preparation of the compound according to claim 1 , comprising the reaction steps:
a) synthesis of the skeleton of compound (1) or (1A) which as yet contains no group (Het-Ar) and/or Ar; and
b) reacting the skeleton from a) in a C—C coupling or C—N coupling.
12. The process as claimed in claim 1 , wherein the C—C coupling is Suzuki, Negishi, Yamamoto, Grignard-Cross or Stille coupling, or the C—N coupling is Buchwald or Ullmann coupling.
13. An oligomer, polymer or dendrimer containing one or more of the compounds according to claim 1 , where one or more bonds from the compound to the polymer, oligomer or dendrimer are present instead of substituents at one or more positions.
14. A formulation comprising at least one of the compound according to claim 1 and at least one solvent.
15. A formulation comprising the oligomer, polymer or dendrimer according to claim 13 and at least one solvent.
16. An electronic device comprising at least one of the compound according to claim 1 .
17. An electronic device comprising the oligomer, polymer or dendrimer according to claim 11 .
18. The electronic device as claimed in claim 17 wherein the device is selected from the group consisting of an organic electroluminescent device, an organic integrated circuit, an organic field-effect transistor, an organic thin-film transistor, an organic light-emitting transistor, an organic solar cell, a dye-sensitised organic solar cell, an organic optical detector, an organic photoreceptor, an organic field-quench device, a light-emitting electrochemical cell, an organic laser diode and an organic plasmon emitting device.
19. An organic electroluminescent device which comprises the compound according to claim 1 is employed as matrix material for phosphorescent or fluorescent emitters and/or in an electron-blocking or exciton-blocking layer and/or in a hole-transport layer and/or in a hole-blocking layer and/or in a hole-blocking or electron-transport layer.