Materials for electronic devices
The present adventure relates to novel compounds of the formula (I) or (II), to the use of the compounds in electronic devices, to a process for the preparation of the compounds, and to electronic devices comprising the compounds, preferably as matrix materials or as electron-transport materials.
1. A compound of formula (II-1a)
where the symbols and indices occurring are defined as follows:
Ar 2 is on each occurrence, identically or differently, an aromatic ring system having 6 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R 1 ;
Ar 3 is on each occurrence, identically or differently, a heteroaromatic ring system having 5 to 30 aromatic ring atoms, which is optionally substituted by one or more radicals R 1 ;
X is selected on each occurrence, identically or differently, and is —B(R 1 )—, —N(R 1 )—, —P(R 1 )—, —P(R 1 ) 3 —, —P(═O)(R 1 )—, —C(R 1 ) 2 —, —Si(R 1 ) 2 —, C═O, C═NR 1 , C═C(R 1 ) 2 , —O—, —S—, —Se—, —S(═O)— or —S(═O) 2 —;
Y is on each occurrence, identically or differently, CR Cz or N, or is C if a group X or Ar 1 or Ar 3 or Cz is bonded to this group;
Z is on each occurrence N;
x is on each occurrence, identically or differently, 0 or 1, where, in the case where x=0, the two groups bonded to the group X in question are bonded directly to one another;
R 1 , R HetAr and R Cz are on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R 2 ) 2 , CN, NO 2 , Si(R 2 ) 3 , B(OR 2 ) 2 , C(═O)R 2 , P(═O)(R 2 ) 2 , S(═O) 2 R 2 , OSO 2 R 2 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R 2 , where one or more CH 2 groups is optionally replaced by —R 2 C═CR 2 —, —Si(R 2 ) 2 —, —Ge(R 2 ) 2 —, —Sn(R 2 ) 2 —, C═O, C═S, C═Se, C═NR 2 , —P(═O)(R 2 )—, —S(═O)—, —S(═O) 2 —, —N(R 2 )—, —O—, —S—, —C(═O)O— or —C(═O)NR 2 —, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which is optionally in each case be substituted by one or more radicals R 2 , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , 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 2 ; two or more substituents R 1 , R HetAr or R Cz here is optionally linked to one another and may optionally form a mono- or polycyclic aliphatic, aromatic or heteroaromatic ring system;
R 2 is on each occurrence, identically or differently, H, D or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms is optionally replaced by D or F; two or more radicals R 2 here is optionally linked to one another and may optionally form a mono- or polycyclic aliphatic, aromatic or heteroaromatic ring system.
2. The compound according to claim 1 , wherein no groups Y, or one or two groups Y, per six-membered ring of the carbazole derivative stand for N, and all other groups Y stand for CR Cz or C.
3. The compound according to claim 1 , wherein for the formula (II-1a) one or more groups Y stand for N.
4. The compound according to claim 1 , wherein X is selected on each occurrence, identically or differently, from N(R 1 ), C(R 1 ) 2 , C═O, C═NR 1 , O, S, S(═O) and S(═O) 2 .
5. A process for the preparation of the compound according to claim 1 , which comprises the following steps:
a) synthesis of a substituted carbazole derivative, optionally with introduction of halogen substituents,
b) coupling of the nitrogen atom of the carbazole derivative to an aryl or heteroaryl group in an organometallic coupling reaction or a nucleophilic aromatic substitution reaction,
c) organometallic coupling reaction for the introduction of aryl or heteroaryl groups on one or both aromatic six-membered rings of the carbazole group.
6. An oligomer, polymer or dendrimer comprising one or more compounds according to claim 1 , where a bond to the polymer, oligomer or dendrimer occurs instead of one or more radicals or H atoms of the compounds.
7. A formulation comprising at least one compound according to claim 1 and at least one solvent.
8. A formulation comprising the oligomer, polymer or dendrimer according to claim 6 and at least one solvent.
9. An electronic device which comprises the compounds according to claim 1 .
10. An electronic device which comprises the oligomer, dendrimer or polymer according to claim 6 .
11. The electronic device as claimed in claim 9 , wherein the device is an organic electroluminescent device (OLED), organic field-effect transistor (O-FET), organic thin-film transistor (O-TFT), organic light-emitting transistor (O-LET), organic integrated circuit (O-IC), organic solar cell (O-SC), organic field-quench device (O-FQD), light-emitting electrochemical cell (LEC), organic laser diode (O-laser) or organic photoreceptor.
12. An organic electroluminescent device which comprises the compound according to claim 1 is employed as a matrix material.
13. An organic electroluminescent device which comprises the compound according to claim 1 is employed as a matrix material for phosphorescent dopants, or as electron-transport material.
14. An organic electroluminescent device comprising a compound of Formula II as a matrix material
where the symbols and indices occurring are defined as follows:
Ar 2 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 6 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 1 ;
Ar 3 is on each occurrence, identically or differently, an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 1 ;
A is N or P;
X is selected on each occurrence, identically or differently, and is —B(R 1 )—, —N(R 1 )—, —P(R 1 )—, —P(R 1 ) 3 —, —C(R 1 ) 2 —, —Si(R 1 ) 2 —, C═O, C═NR 1 , C═C(R 1 ) 2 , —O—, —S—, —Se—, —S(═O)— or —S(═O) 2 —;
Y is on each occurrence, identically or differently, CR Cz or N, or is C if a group X or Ar 1 or Ar 3 or Cz is bonded to this group;
Z is on each occurrence, identically or differently, CR HetAr or N, where at least one Z per six-membered ring is equal to N;
q is on each occurrence, identically or differently, 0 or 1, where, in the case where q=0, the two groups bonded to the group Ar 1 or Ar 3 in question are bonded directly to one another;
s is on each occurrence, identically or differently, 0 or 1, with the proviso that at least one index s is equal to 1;
x is on each occurrence, identically or differently, 0 or 1, where, in the case where x=0, the two groups bonded to the group X in question are bonded directly to one another;
R 1 , R HetAr and R Cz are on each occurrence, identically or differently, H, D, F, Cl, Br, I, N(R 2 ) 2 , CN, NO 2 , Si(R 2 ) 3 , B(OR 2 ) 2 , C(═O)R 2 , P(═O)(R 2 ) 2 , S(═O)R 2 , S(═O) 2 R 2 , OSO 2 R 2 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a straight-chain alkenyl or alkynyl group having 2 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R 2 , where one or more CH 2 groups is optionally replaced by —R 2 C═CR 2 —, —Si(R 2 ) 2 —, —Ge(R 2 ) 2 —, —Sn(R 2 ) 2 —, C═O, C═S, C═Se, C═NR 2 , —P(═O)(R 2 )—, —S(═O)—, —S(═O) 2 —, —N(R 2 )—, —O—, —S—, —C(═O)O— or —C(═O)NR 2 —, or an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which is optionally in each case be substituted by one or more radicals R 2 , or an aryloxy or heteroaryloxy group having 5 to 60 aromatic ring atoms, which is optionally substituted by one or more radicals R 2 , 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 2 ; two or more substituents R 1 , R HetAr or R Cz here is optionally linked to one another and may optionally form a mono- or polycyclic aliphatic, aromatic or heteroaromatic ring system;
R 2 is on each occurrence, identically or differently, H, D or an aliphatic, aromatic or heteroaromatic organic radical having 1 to 20 C atoms, in which, in addition, one or more H atoms is optionally replaced by D or F; two or more radicals R 2 here is optionally linked to one another and may optionally form a mono- or polycyclic aliphatic, aromatic or heteroaromatic ring system.
15. The electroluminescent device according to claim 14 , wherein no groups Y, or one or two groups Y, per six-membered ring of the carbazole derivative stand for N, and all other groups Y stand for CR Cz or C.
16. The electroluminescent device according to claim 14 , wherein A is N.
17. The electroluminescent device according to claim 14 , wherein one or more groups Y is N.
18. The electroluminescent device according to claim 14 , wherein all indices s adopt the value 1.
19. The electroluminescent device according to claim 14 , wherein the group
of the formula (II) represents triazine, pyrazine, pyridazine, pyrimidine or pyridine, which is optionally substituted by one or more radicals R HetAr .
20. The electroluminescent device according to claim 14 , wherein X is on each occurrence, identically or differently, selected from N(R 1 ), C(R 1 ) 2 , C═O, C═NR 1 , O, S, S(═O) or S(═O) 2 .
21. The electroluminescent device according to claim 14 , wherein the compound conforms to one of the following formulae:
where the symbols and indices occurring are as defined in claim 14 .