Spirobifluorene compounds for organic electroluminescent devices
The present invention relates to spirobifluorene compounds of the formula (1) which are suitable for use in electronic devices, in particular organic electroluminescent devices, and to electronic devices which comprise these compounds.
1. A compound of formula (1):
wherein
Ar 1 and Ar 2 are, identically or differently on each occurrence, selected from formulae (11) to (66)
where the dashed bond indicates the bond to the nitrogen, and the groups may be substituted by one or more radicals R 5 ;
Ar S is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 6 to 60 C atoms, which may in each case also be substituted by one or more radicals R 5 ;
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, Si(R 6 ) 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, each of which may be substituted by one or more radicals R 6 , where in each case one or more non-adjacent CH 2 groups may be replaced by Si(R 6 ) 2 , C═NR 6 , P(═O)(R 6 ), SO, SO 2 , NR 6 , O, S or CONR 6 and where one or more H atoms may be replaced by D, F, Cl, Br or I, an aromatic or heteroaromatic ring system having 6 to 60 C atoms, which may in each case be substituted by one or more radicals R 6 , an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 6 , or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 6 , where two or more adjacent substituents R 1 or R 2 or R 3 or R 4 may optionally form a mono- or polycyclic, aliphatic ring system, which may be substituted by one or more radicals R 6 ;
R 5 is selected on each occurrence, identically or differently, from the group consisting of H, D, F, Cl, Br, I, CN, Si(R 6 ) 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, each of which may be substituted by one or more radicals R 6 , where in each case one or more non-adjacent CH 2 groups may be replaced by Si(R 6 ) 2 , C═NR 6 , P(═O)(R 6 ), SO, SO 2 , NR 6 , O, S or CONR 6 and where one or more H atoms may be replaced by D, F, Cl, Br or I, an aromatic or heteroaromatic ring system having 6 to 60 C atoms, which may in each case be substituted by one or more radicals R 6 , an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R 6 , or an aralkyl or heteroaralkyl group having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R 6 , where two or more adjacent substituents R 5 may optionally form a mono- or polycyclic, aliphatic ring system, which may be substituted by one or more radicals R 6 ;
R 6 is selected from the group consisting of H, D, F, an aliphatic hydrocarbon radical having 1 to 20 C atoms or an aromatic or heteroaromatic ring system having 5 to 30 C atoms, in which one or more H atoms may be replaced by D or F, where two or more adjacent substituents R 6 may form a mono- or polycyclic, aliphatic ring system with one another;
i is on each occurrence, identically or differently, 0 or 1;
m is 0, 1 or 2;
n is on each occurrence, identically or differently, 0, 1, 2, 3 or 4;
p, q are 0; and
r, s are on each occurrence, identically or differently, 0, 1, 2, 3 or 4, where p+r≤4 and q+s≤4.
2. The compound according to claim 1 , wherein the index i is 0.
3. The compound according to claim 1 , wherein the compound is a compound of formulae (2), (5) or (8),
where the symbols and indices used are defined as in claim 1 .
4. The compound according to claim 1 , wherein the compound is a compound of formulae (2a), (5a) or (8a),
where the symbols and indices used are defined as in claim 1 .
5. The compound according to claim 1 , wherein the compound is a compound of formulae (2b), (5b) or (8b),
where the symbols used are defined as in claim 1 .
6. The compound according to claim 1 , wherein groups Ar 1 and Ar 2 are, identically or differently on each occurrence, selected from the group consisting of the formulae (11), (13), (16), (20), (28), (29), (33), (34), (35), (37), (38), (39), (40), (44), (48), (49), (51), and (59).
7. The compound according to claim 1 , wherein groups Ar 1 and Ar 2 are, identically or differently on each occurrence, selected from the group consisting of the formulae (11), (13), (20), (29), (35), (38), (39), (49), (51), and (59).
8. The compound according to claim 1 , wherein the groups Ar 1 and Ar 2 are selected identically.
9. The compound according to claim 1 , wherein R 1 to R 4 are selected, identically or differently on each occurrence, from the group consisting of H, F, CN, 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, each of which may be substituted by one or more radicals R 6 , 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 F, 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 6 .
10. The compound according to claim 1 , wherein the radical R 5 which is bonded to Ar 1 or Ar 2 or Ar S is selected, identically or differently on each occurrence, from the group consisting of H, F, CN, a straight-chain alkyl group having 1 to 10 C atoms, a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which may be substituted by one or more radicals R 6 .
11. The compound according to claim 1 , wherein
R 1 to R 4 are selected, identically or differently on each occurrence, from the group consisting of H, F, CN, 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, each of which may be substituted by one or more radicals R 6 , 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 F, 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 6 ;
R 5 is, if the radical R 5 is bonded to Ar 1 or Ar 2 or Ar S , selected, identically or differently on each occurrence, from the group consisting of H, F, CN, a straight-chain alkyl group having 1 to 10 C atoms, a branched or cyclic alkyl group having 3 to 10 C atoms or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, each of which may be substituted by one or more radicals R 6 ;
or R 5 which is bonded to the carbon bridge in the formulae (20) to (23), (53), (54), (68) and (72) is, identically or differently, an alkyl group having 1 to 10 C atoms, in particular methyl, or a phenyl group, which may be substituted by one or more radicals R 6 ;
or R 5 which is bonded to the nitrogen bridge in the formulae (28) to (31), (40) to (43) or (55) to (58), (63) to (66), (71) and (73) is a phenyl group, which may be substituted by one or more radicals R 6 ;
R 6 is selected on each occurrence, identically or differently, from the group consisting of H, 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 24 C atoms;
i is 0;
m is 0 or 1;
n is 0 or 1;
r is 0 or 1; and
s is 0 or 1.
12. A process for the preparation of the compound according to claim 1 comprising introducing a diarylamino group by a C—N coupling reaction between a 1- or 3- or 4-halogenated spirobifluorene and a dirarylamine, and thereby producing the compound of claim 1 .
13. A method comprising providing the compound according to claim 1 , and incorporating the compound in an electronic device.
14. An electronic device comprising at least one compound according to claim 1 , 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 devices, and wherein the compound is comprised as hole-transport material in a hole-transport or hole-injection or exciton-blocking or electron-blocking layer, or is comprised as matrix material for fluorescent or phosphorescent emitters in an emitting layer.