Materials for organic electroluminescent devices
The present invention relates to 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 the formula (5) or (6),
where
R 40 , R 41 , R 43 , R 44 are at each occurrence, identically or differently, selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R 32 , 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 32 ,
R 42 is selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R 32 , or an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one more radicals R 32 ; and
R A stands on each occurrence, identically or differently, for F, CN, a straight-chain alkyl or alkoxy group having 1 to 40 C atoms or branched or cyclic alkyl or alkoxy groups having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where one or more H atoms may be replaced by D or F; or 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;
or
R 40 , R 41 , R 43 , R 44 are at each occurrence, identically or differently, selected from an aromatic ring system having 6 to 30 aromatic ring atoms, which may in each case be substituted by one or more radicals R 32 ;
R 42 is selected from H, a straight-chain alkyl group having 1 to 10 carb atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R 32 , 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 32 ; and
R A stands on each occurrence, identically or differently, for H, D, F, CN, a straight-chain alkyl or alkoxy group having 1 to 40 C atoms or branched or cyclic alkyl or alkoxy groups having 3 to 40 C atoms, each of which may be substituted by one or more radicals R, where one or more H atoms may be replaced by D or F; or 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;
Y is a single bond or a divalent bridge selected from —C(R Y ) 2 —, —C(R Y ) 2 —C(R Y ) 2 —, —O—, —S—, —S(═O) 2 — and —C(═O)—;
R Y stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, N(Ar) 2 , C(═O)Ar, P(═O)(Ar) 2 , S(═O)Ar, S(═O) 2 Ar, NO 2 , N(R) 2 , Si(R) 3 , B(OR) 2 , OSO 2 R, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms, each of which may be substituted by one or more radicals R, where in each case one or more non-adjacent CH 2 groups may be replaced by RC═CR, C≡C, Si(R) 2 , Ge(R) 2 , Sn(R) 2 , C═O, C═S, C═Se, P(═O)(R), SO, SO 2 , O, S or CONR and where one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 , or 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, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R, or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms, which may be substituted by one or more R radicals; where two adjacent substituents R Y may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R′;
R 32 is on each occurrence, identically or differently, selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or an aromatic ring system having 6 to 24 aromatic ring atoms;
R stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CHO, CN, N(Ar) 2 , C(═O)Ar, P(═O)(Ar) 2 , S(═O)Ar, S(═O) 2 Ar, NO 2 , Si(R′) 3 , B(OR′) 2 , OSO 2 R, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl groups having 3 to 40 C atoms, each of which may be substituted by one or more radicals R′, where in each case one or more non-adjacent CH 2 groups may be replaced by R′C═CR′, C≡C, Si(R′) 2 , Ge(R′) 2 , Sn(R′) 2 , C═O, C═S, C═Se, P(═O)(R′), SO, SO 2 , O, S or CONR′ and where one or more H atoms may be 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′, or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more radicals R′, where two adjacent radicals R may form a mono- or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more radicals R′;
Ar is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may in each case also be substituted by one or more radicals R′;
R′ stands on each occurrence, identically or differently, for H, D, F, Cl, Br, I, CN, a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atoms or branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms, where in each case one or more non-adjacent CH 2 groups may be replaced by SO, SO 2 , O, S and where one or more H atoms may be replaced by D, F, Cl, Br or I, or an aromatic or heteroaromatic ring system having 5 to 24 C atoms.
2 . The compound according to claim 1 , wherein R A stand on each occurrence, identically or differently,
for H, D, F, CN; or
for a group of formula (RS-a),
wherein
R 22 , R 23 , R 24 are at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R 25 , and where two of radicals R 22 , R 23 , R 24 or all radicals R 22 , R 23 , R 24 may be joined to form a (poly) cyclic alkyl group, which may be substituted by one or more radicals R 25 ;
R 25 is at each occurrence, identically or differently, selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms;
with the proviso that at each occurrence at least one of radicals R 22 , R 23 and R 24 is other than H, with the proviso that at each occurrence all of radicals R 22 , R 23 and R 24 together have at least 4 carbon atoms and with the proviso that at each occurrence, if two of radicals R 22 , R 23 , R 24 are H, the remaining radical is not a straight-chain;
or for a group of formula (RS-b),
wherein
R 26 , R 27 , R 28 are at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R 25 as defined above, and where two of radicals R 26 , R 27 , R 28 or all radicals R 26 , R 27 , R 28 may be joined to form a (poly) cyclic alkyl group, which may be substituted by one or more radicals R 25 as defined above;
with the proviso that at each occurrence only one of radicals R 26 , R 27 and R 28 may be H;
or for a group of formula (RS-d),
wherein
R 40 to R 44 is at each occurrence, identically or differently, selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R 32 , 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 32 , and where two or more of radicals R 40 to R 44 may be joined to form a (poly) cyclic alkyl group or an aromatic ring system, each of which may be substituted by one or more radicals R 32 as defined above;
or for a group of formula (ArL-1),
where the dashed bond in formula (ArL-1) indicates the bonding to the structure of formula (15) or (6), where Ar2, Ar3 stand on each occurrence, identically or differently, for an aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R; and where m is an integer selected from 1 to 10.
3 . The compound according to claim 1 , wherein the compound is selected from the compounds of formulae (5-2) and (5-3),
where the group R A has the same meaning as in claim 1 , and where in each of formulae (5-2) and (5-3) the phenyl groups indicated with —R 32 are unsubstituted or substituted with one or more radicals R 32 ;
R 42 is selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R 32 ;
R 32 is at each occurrence, identically or differently, selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or an aromatic ring system having 6 to 24 aromatic ring atoms.
4 . The compound according to claim 1 , wherein the compound is selected from the compounds of formulae (5-2-Y1) to (5-3-Y7),
where the groups R A , R Y and R have the same meaning as in claim 1 , and where in each of formulae (5-1-Y1) to (5-3-Y7), the phenyl groups indicated with —R 32 are unsubstituted or substituted with one or more radicals R 32 ;
R 42 is selected from H, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R 32 ;
R 32 is at each occurrence, identically or differently, selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or an aromatic ring system having 6 to 24 aromatic ring atoms.
5 . The compound according to claim 1 , wherein the groups R 40 , R 42 , R 44 are at each occurrence, identically or differently, selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, where the above-mentioned groups may each be substituted by one or more radicals R 32 ,
R 32 is at each occurrence, identically or differently, selected from a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, or an aromatic ring system having 6 to 24 aromatic ring atoms.
6 . A process for the preparation of the compound according to claim 1 , comprising the following steps:
(i) cyclisation reaction of a triarylamine compound substituted by at least one boronic acid or ester group, in the presence of a halide compound, so that the boron atom of the boronic acid or ester group forms a six-membered ring with an adjacent aromatic or heteroaromatic group present in the triarylamine and where the boron atom is further substituted by a halogen;
(ii substitution reaction between the halogenated boron compound obtained in step (i) and a metal organyl reactant so that the halogen group on the boron atom is replaced by an organic group.
7 . A polymer, oligomer or dendrimer containing one or more compounds according to claim 1 .
8 . A formulation comprising at least one compound according to claim 1 and at least one solvent.
9 . 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, dye-sensitised organic solar cells, organic optical detectors, organic photoreceptors, organic field-quench devices, light-emitting electrochemical cells, organic laser diodes and organic plasmon emitting devices.
10 . An organic electroluminescent device comprising at least one compound according to claim 1 , wherein the compound is employed as an emitter in an emitting layer.
11 . The organic electroluminescent device according to claim 10 , wherein the compound is employed as a fluorescent emitter in an emitting layer, wherein the emitting layer comprises at least one further component selected from matrix materials.
12 . The organic electroluminescent device according to claim 10 , wherein the compound is employed as an emitter showing Thermally Activated Delayed Fluorescence in an emitting layer, wherein the emitting layer comprises at least one further component selected from matrix materials.
13 . The organic electroluminescent device according to claim 10 , wherein the compound is employed as a fluorescent emitter in an emitting layer, wherein the emitting layer comprises at least one sensitizer selected from phosphorescent compounds and thermally activated delayed fluorescence compounds.
14 . The organic electroluminescent device according to claim 13 , wherein the emitting layer further comprises at least one organic functional material selected from matrix materials.