Materials for organic electroluminescent devices
The present invention relates to electron-deficient heteroaromatic compounds which are substituted by dibenzofuran or dibenzothiophene derivatives and by carbazoles or amines, in particular for use as triplet matrix materials in organic electroluminescent devices. The invention furthermore relates to a process for the preparation of the compounds according to the invention and to electronic devices comprising these compounds.
1. A compound of the formula (1),
where:
A is on each occurrence, identically or differently, CR 1 or N, where a maximum of two groups A per ring stand for N;
Y 1 is O or S;
L is on each occurrence, identically or differently, a single bond or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R 1 ;
HetAr is a group of the formula (2) or ( 3 ),
where the dashed bonds represent the it ung of this group to the dibenzofuran or dibenzothiophene derivative and to L;
X is on each occurrence, identically or differently, CR 2 or N, with the proviso that at least one symbol X stands for N;
N 1 is a group of the following formula (4), (5) or (6),
where the dashed bond represents the linking of this group to L;
Ar 1 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more radicals R 3 ;
W is on each occurrence, identically or differently, CR 1 or N, where a maximum of two groups W stand for N, or two adjacent groups W together stand for a group of the following formula (7) or (8), where the group of the formula (4) or (6) contains a maximum of one group of the formula (7) or (8), and the remaining groups W stand, identically or differently on each occurrence, for CR 1 or N,
where the dashed bonds indicate the linking of this group, and A has the meanings given above;
Y 2 , Y 3 are, identically or differently on each occurrence, O, NR 4 , S, C(R 4 ) 2 , Si(R 4 ) 2 , BR 4 or C═O, where the radical R 4 which is bonded to N is not equal to H;
R 1 , R 2 , R 3 , R 4 are selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, NO 2 , N(Ar 2 ) 2 , N(R 5 ) 2 , C(═O)Ar 2 , C(═O)R 5 , P(═O)(Ar 2 ) 2 , P(Ar 2 ) 2 , B(Ar 2 ) 2 , Si(Ar 2 ) 3 , Si(R 5 ) 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 group having 2 to 20 C atoms, each of which may be substituted by one or more radicals R 5 , where one or more non-adjacent CH 2 groups may be replaced by R 5 C═CR 5 , Si(R 5 ) 2 , C═O, C═NR 5 , P(═O)(R 5 ), SO, SO 2 , NR 5 , O, S or CONR 5 and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 , an aromatic or heteroaro-matic ring system having 5 to 40 aromatic ring atoms, which may in each case be substituted by one or more radicals R 5 , an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R 5 , or an aralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms, which may be substituted by one or more radicals R 5 ; two adjacent substituents R 1 or two adjacent substituents R 3 or two adjacent substituents R 4 here may optionally form an aliphatic, aromatic or heteroaromatic ring system with one another, which may be substituted by one or more radicals R 5 ;
Ar 2 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more non-aromatic radicals R 5 ; two radicals Ar 2 which are bonded to the same N atom, P atom or B atom here may also be bridged to one another by a single bond or a bridge selected from N(R 5 ), C(R 5 ) 2 , O or S;
R 5 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 may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups, each having 1 to 4 carbon atoms; two or more adjacent substituents R 5 here may form an aliphatic ring system with one another;
with the proviso that Y 1 stands for O if the group N 1 stands for a group of the formula (4) which does not contain a group of the formula (7) or (8)
with the proviso that compounds are excluded wherein HetAr is a group of formula (2) and N 1 is a group of formula (4), which does not comprise a group of formula (7) or formula (8).
2. The compound according to claim 1 of the formula (1a),
where the symbols used have the meanings given in claim 1 , n stands for 0, 1, 2 or 3 and m stands for 0, 1, 2, 3 or 4.
3. The compound according to claim 1 of one of the formulae (1b) to (1i),
where symbols used have the meanings given in claim 1 .
4. The compound according to claim 1 , wherein the groups of the formula (2) and (3) are selected from the groups of the formulae (2-1) to (2-7) and (3-1),
where the dashed bond and * represents the linking of these groups to the dibenzofuran or dibenzothiophene derivative in formula (1), the dashed bond and # represents the linking of these groups to L or, for L equal to a single bond, to N 1 , and R 2 has the meanings given in claim 1 .
5. The compound according to claim 1 , wherein the groups of the formulae (2) and (3) are selected from the groups of the formulae (2-1a) to (3-1a),
where the dashed bond and * represents the linking of these groups to the dibenzofuran ter dibenzothiophene derivative in foiniula (1), the dashed bond and # represents the linking of these groups to L or, for L equal to a single bond, to N I , and R 2 stands for H or an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may be substituted by one or more radicals R 5 .
6. The compound according to claim 1 , wherein the groups of the formulae (4) and (6) are selected from the groups of the formulae (4-1), (4-2) and (6-1),
where R 1 and m have the meanings given in claim 1 , and furthermore:
two adjacent groups W together stand for a group of the formula (7a) or (8a) and the other two groups W stand for CR 1 ,
where Y 2 , Y 3 , R 1 and m have the meanings given in claim 1 .
7. The compound according to claim 6 , wherein the group of the formula (4-1) is selected from the groups of the formulae (4-1a) to (4-1f) and in that the group of the formula (4-2) is selected from the groups of the formulae (4-2a) to (4-2f),
where symbols and indices used have the meanings given in claim 1 .
8. The compound according to claim 1 , wherein Ar 1 in the group of the formula (5) stands, identically or differently on each occurrence, for an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R 3 .
9. The compound according to claim 1 , wherein R 1 is selected from the group consisting of H, D, F, CN, N(Ar 2 ) 2 , C(═O)(Ar 2 , P(═O)(Ar 2 ) 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 group having 2 to 10 C atoms, each of which may be substituted by one or more radicals R 5 , where one or more non-adjacent CH 2 groups may be replaced by O and where one or more H atoms may be replaced by D or F, an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R 5 , or an aralkyl or heteroaralkyl group having 5 to 25 aromatic ring atoms, which may be substituted by one or more radicals R 1 ; two substituents R 1 which are bonded to adjacent carbon atoms here may optionally form a monocyclic or polycyclic, aliphatic ring system, which may be substituted by one or more radicals R 5 .
10. The compound according to claim 1 for which:
Y 1 is O or S;
L is on each occurrence, identically or differently, a single bond or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may be substituted by one or more radicals R 1 ;
HetAr is a group of one of the formulae (2-1) to (2-7) or (3-1) according to claim 4 ;
N 1 is a group of the formula (4-1), (4-2), (5) or (6-1),
two adjacent groups W together stand for a group of the formula (7a) or (8a) and the other two groups W stand for CR 1 ,
Ar 1 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 6 to 24 aromatic ring atoms, preferably having 6 to 18 aromatic ring atoms, which may be substituted by one or more radicals R 3 ;
Y 2 , Y 3 are, identically or differently on each occurrence, O, S, NR 4 or C(R 4 ) 2 , where the radical R 4 which is bonded to N is not equal to H;
R 1 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, N(Ar 2 ) 2 , C(═O)Ar 2 , P(═O)(Ar 2 ) 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 group having 2 to 10 C atoms, each of which may be substituted by one or more radicals R 5 , where one or more non-adjacent CH 2 groups may be replaced by O and where one or more H atoms may be replaced by D or F, an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R 5 , or an aralkyl or heteroaralkyl group having 5 to 25 aromatic ring atoms, which may be substituted by one or more radicals R 1 ; two substituents R 1 which are bonded to adjacent carbon atoms here may optionally form a monocyclic or polycyclic, aliphatic ring system, which may be substituted by one or more radicals R 5 ;
R 2 is on each occurrence, identically or differently, H or an aromatic or hetero-aromatic ring system having 6 to 24 aromatic ring atoms, in particular having 6 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R 5 ;
R 3 is on each occurrence, identically or differently, H, an alkyl group having 1 to 4 C atoms or an aromatic or heteroaromatic ring system having 5 to 14 aromatic ring atoms;
R 4 is, for Y 2 or Y 3 =NR 4 , an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R 5 ;
and is, for Y 2 or Y 3 =C(R 4 ) 2 , on each occurrence, identically or differently, 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 alkenyl group having 2 to 10 C atoms, each of which may be substituted by one or more radicals R 5 , where one or more non-adjacent CH 2 groups may be replaced by O and where one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may in each case be substituted by one or more radicals R 5 ; the two substituents R 4 here may optionally foiiii a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system, which may be sub-stituted by one or more radicals R 5 ;
R 5 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, CN, an aliphatic hydrocarbon radical having 1 to 10 C atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted by one or more alkyl groups, each having 1 to 4 carbon atoms;
the other symbols and indices have the meanings given in claim 1 .
11. A process for the preparation of a compound according to claim 1 , starting from an optionally substituted 1-halodibenzofuran or 1-halodibenzothiophene, comprising the following steps:
a) optionally conversion of the halogen group into a boronic acid or a boronic acid derivative;
b) introduction of the group HetAr by a coupling reaction;
c) introduction of the group N 1 or the group -L-N 1 by a coupling reaction.
12. A formulation comprising at least one compound according to claim 1 and at least one further compound and/or a solvent.
13. A method comprising utilizing the compound according to claim 1 or the formulation according to claim 12 in an electronic device.
14. An electronic device comprising at least one compound according claim 1 or the formulation according to claim 12 , wherein the electronic devise 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.
15. The electronic device according to claim 14 , wherein the device is an organic electroluminescent device and wherein the compound according to claim 1 is employed as matrix material for fluorescent or phosphorescent emitters in an emitting layer and/or in an electron-transport layer and/or in an electron-blocking or exciton-blocking layer and/or in a hole-transport layer.