Spirobifluorene derivative-based materials for electronic devices
The present application relates to spirobifluorene derivatives of a formula (I), to the use thereof in electronic devices, and to processes for preparing said derivatives.
1. A compound of the formula (I)
which is optionally substituted at one or more positions shown as unsubstituted in the base structure of formula (I) by one R 1 radical each; and
which has the following definitions of the variables:
Y is selected from a single bond, O, S and Se;
Z is selected from O, S and Se;
E is the same or different at each instance and is a single bond or an aromatic or heteroaromatic ring system which has 6 to 30 aromatic ring atoms and is optionally substituted by one or more R 2 radicals;
A is the same or different at each instance and is a group of the formula (A1), (A2) or (A3) which is bonded via the bond marked with #;
wherein
N is a nitrogen atom,
Ar 2 is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 6 to 30 aromatic ring atoms and is optionally substituted by one or more R 2 radicals;
X is the same or different at each instance and is a single bond or a group selected from BR 2 , C(R 2 ) 2 , Si(R 2 ) 2 , C═O, O, S, S═O, SO 2 , NR 2 , PR 2 and P(═O)R 2 ;
R 1 is the same or different at each instance and is selected from H, D, F, C(═O)R 3 , CN, Si(R 3 ) 3 , P(═O)(R 3 ) 2 , OR 3 , S(═O)R 3 , S(═O) 2 R 3 , straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R 1 radicals is optionally joined to one another and optionally forms a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned optionally each is substituted by one or more R 3 radicals; and where one or more CH 2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned is optionally replaced by —R 3 C═CR 3 —, —C≡C—, Si(R 3 ) 2 , C═O, C═NR 3 , —C(═O)O—, —C(═O)NR 3 —, NR 3 , P(═O)(R 3 ), —O—, —S—, SO or SO 2 ;
R 2 is the same or different at each instance and is selected from H, D, F, C(═O)R 3 , CN, Si(R 3 ) 3 , N(R 3 ) 2 , P(═O)(R 3 ) 2 , OR 3 , S(═O)R 3 , S(═O) 2 R 3 , straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R 2 radicals is optionally joined to one another and optionally forms a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned optionally each is substituted by one or more R 3 radicals; and where one or more CH 2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned is optionally replaced by —R 3 C═CR 3 —, —C≡C—, Si(R 3 ) 2 , C═O, C═NR 3 , —C(═O)NR 3 —, NR 3 , P(═O)(R 3 ), —O—, —S—, SO or SO 2 ;
R 3 is the same or different at each instance and is selected from H, D, F, C(═O)R 4 , CN, Si(R 4 ) 3 , N(R 4 ) 2 , P(═O)(R 4 ) 2 , OR 4 , S(═O)R 4 , S(═O) 2 R 4 , straight-chain alkyl or alkoxy groups having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms, and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R 1 or R 2 radicals is optionally joined to one another and optionally forms a ring; where the alkyl, alkoxy, alkenyl and alkynyl groups mentioned and the aromatic ring systems and heteroaromatic ring systems mentioned optionally each is substituted by one or more R 4 radicals; and where one or more CH 2 groups in the alkyl, alkoxy, alkenyl and alkynyl groups mentioned is optionally replaced by —R 4 C═CR 4 —, —C≡C—, Si(R 4 ) 2 , C═O, C═NR 4 , —C(═O)O—, —C(═O)NR 4 —, NR 4 , P(═O)(R 4 ), —O—, —S—, SO or SO 2 ;
R 4 is the same or different at each instance and is selected from H, D, F, CN, alkyl groups having 1 to 20 carbon atoms, aromatic ring systems having 6 to 40 aromatic ring atoms and heteroaromatic ring systems having 5 to 40 aromatic ring atoms; where two or more R 4 radicals is optionally joined to one another and optionally forms a ring; and where the alkyl groups, aromatic ring systems and heteroaromatic ring systems mentioned is optionally substituted by F or CN;
q is the same or different at each instance and is 0 or 1, where at least one q in formula (A2) is 1;
a, b, c, and d are the same or different at each instance and are 0 or 1, where at least one of the indices a, b, c and d is 1, and where, in the case that one or more of the indices a, b, c and d are 0, an R 1 group is attached at the position in question.
2. The compound according to claim 1 , wherein Y is a single bond and Z is O or S.
3. The compound according to claim 1 , wherein Y is O and S and Z is O or S.
4. The compound according to claim 1 , wherein E is the same or different at each instance and is selected from a single bond and a divalent group derived from benzene, biphenyl, terphenyl, fluorene, spirobifluorene, indenofluorene, carbazole, dibenzofuran or dibenzothiophene, each optionally substituted by R 2 radicals, or a combination of two or more of these groups, where not more than 30 aromatic ring atoms are present in the E group.
5. The compound according to claim 1 , wherein X is a single bond.
6. The compound according to claim 1 , wherein A is the same or different at each instance and is a group of the formula (A-1) or (A-3).
7. The compound according to claim 1 , wherein Ar 2 is the same or different at each instance and is selected from phenyl, biphenyl, terphenyl, fluorenyl, spirobifluorenyl, indenofluorenyl, naphthyl, phenanthrenyl, furanyl, benzofuranyl, dibenzofuranyl, thiophenyl, benzothiophenyl, dibenzothiophenyl, carbazolyl, indolocarbazolyl and indenocarbazolyl, each of which may be substituted by one or more R 2 radicals.
8. The compound according to claim 1 , wherein R 1 is the same or different at each instance and is selected from H, F, CN, methyl, tert-butyl, phenyl, biphenyl, dibenzofuran, dibenzothiophene and carbazole.
9. The compound according to claim 1 , wherein R 1 is H.
10. The compound according to claim 1 , wherein exactly one of the indices a, b, c and d is 1 and the other indices are 0; or in that exactly two of the indices a, b, c and d are 1, and the other indices are 0.
11. The compound according to claim 1 , wherein the index d is 0, and in that exactly one or exactly two of the indices a, b and c are 1.
12. The compound according to claim 1 , wherein the compound corresponds to the following embodiment of formula (I-A)
wherein variables that occur are as defined as in claim 1 .
13. A process for preparing the compound of the formula (I) according to claim 1 , which comprises
first preparing a spirobifluorene base skeleton and, in a later step, via an organometallic coupling reaction, an arylamino or carbazole group or an aryl or heteroaryl group substituted by an arylamino or carbazole group is introduced.
14. Oligomers, polymers or dendrimers containing one or more compounds of formula (I) according to claim 1 , wherein the bond(s) to the polymer, oligomer or dendrimer may be localized at any desired positions substituted by R 1 or R 2 in formula (I).
15. A formulation comprising at least one compound according to claim 1 , and at least one solvent.
16. An electronic device comprising at least one compound according to claim 1 .
17. The electronic device according to claim 16 , wherein the device is an organic electroluminescent device comprising anode, cathode and at least one emitting layer, where at least one organic layer of the device, which may be an emitting layer, a hole transport layer or another layer, comprises the at least one compound.
18. The electronic device according to claim 17 , wherein the at least one organic layer is selected from a hole transport layer and an emitting layer.
19. The electronic device according to claim 17 , wherein the at least one organic layer is selected from an electron blocker layer, and an emitting layer comprising one or more phosphorescent emitters.