Heterocyclic compounds with dibenzazapine structures
The present invention relates to heterocyclic compounds and electronic devices, in particular organic electroluminescent devices, containing these compounds.
1. A compound of the formula (II)
where the symbols used are as follows:
X is CR 1 ;
W is a bond;
R 1 is H;
R 2 is the same or different at each instance and is H, D F, Cl, Br, I, B(OR 3 ) 2 , CHO, C(═O)R 3 , CR 3 ═C(R 3 ) 2 , CN, C(═O)OR 3 , C(═O)N(R 3 ) 2 , Si(R 3 ) 3 , N(R 3 ) 2 , NO 2 , P(═O)(R 3 ) 2 , OSO 2 R 3 , OR 3 , S(═O)R 3 , S(═O) 2 R 3 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 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 R 3 radicals, where one or more nonadjacent CH 2 groups may be replaced by —R 3 C═CR 3 —, Si(R 3 ) 2 , Si(R 2 ) 2 , Ge(R 3 ) 2 , Sn(R 3 ) 2 , C═O, C═S, C═Se, C═NR 3 , —C(═O)O—, —C(═O)NR 3 —, NR 3 , P(═O)(R 3 ), —O—, —S—, SO or SO 2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 , or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R 3 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R 3 radicals, or a combination of these systems; at the same time, two or more adjacent R 2 substituents together may also form a mono- or polycyclic, aliphatic or aromatic ring system;
R 3 is the same or different at each instance and is H, F or an aliphatic, aromatic and/or heteroaromatic hydrocarbyl radical having 1 to 20 carbon atoms, in which hydrogen atoms may also be replaced by F; at the same time, two or more adjacent R 3 substituents together may also form a mono- or polycyclic, aliphatic or aromatic ring system;
R a and R b are independently an aromatic group having 10 to 40 carbon atoms or a heteroaromatic group having 6 to 40 carbon atoms, where the aromatic and/or heteroaromatic group comprises at least two adjacent aromatic and/or heteroaromatic rings, each of which may be fused or unfused and/or may be substituted by one or more R 1 ′ radicals, wherein
R 1′ is the same or different at each instance and is H, F, Cl, Br, I, B(OR 2 ) 2 , CHO, C(═O)R 2 , CR 2 ═C(R 2 ) 2 , CN, C(═O)OR 2 , C(═O)N(R 2 ) 2 , Si(R 2 ) 3 , N(R 2 ) 2 , NO 2 , P(═O)(R 2 ) 2 , OSO 2 R 2 , OR 2 , S(═O)R 2 , S(═O) 2 R 2 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 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 R 2 radicals, where one or more nonadjacent CH 2 groups may be replaced by —R 2 C═CR 2 —, —C≡C—, Si(R 2 ) 2 , Ge(R 2 ) 2 , Sn(R 2 ) 2 , C═O, C═S, C═Se, C═NR 2 , —C(═O)O—, —C(═O)NR 2 —, NR 2 , P(═O)(R 2 ), —O—, —S—, SO or SO 2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO 2 , or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R 2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R 2 radicals, or a combination of these systems; at the same time, two or more adjacent R 1 substituents together may also form a mono- or polycyclic, aliphatic or aromatic ring system.
2. A compound as claimed in claim 1 , wherein the compound is a compound of formula (IV)
where for the symbols used have the definition given in claim 1 , and R a and R b are selected independently of each other.
3. A compound as claimed in claim 1 , wherein at least one of the R a and/or R b radicals is a hole transport group or an electron transport group.
4. A compound as claimed in claim 1 , wherein the R b radical in one of the formulae (II), and/or (IV) is a hole transport group and the R a radical in one of the formulae (II), and/or (IV) is a hole transport group.
5. A compound as claimed in claim 1 , wherein the R b radical in one of the formulae (II), and/or (IV) is an electron transport group and the R a radical in one of the formulae (II), and/or (IV) is a hole transport group.
6. A compound as claimed in claim 1 , wherein the R b radical in one of the formulae (II), and/or (IV) is a hole transport group and the R a radical in one of the formulae (II), and/or (IV) is an electron transport group.
7. A compound as claimed in claim 1 , wherein the R b radical in one of the formulae (II), and/or (IV) is an electron transport group and the R a radical in one of the formulae (II), and/or (IV) is an electron transport group.
8. A compound as claimed in claim 1 , wherein, in the structure of formula (I), (II), and/or (IV), at least one R a , and/or R b radical is a group independently selected from the formulae (R 1 -2) to (R 1 -72)
has,
where the symbols used are as follows:
Y is O, S or NR 2 ;
j independently at each instance is 0, 1, 2 or 3;
h independently at each instance is 0, 1, 2, 3 or 4;
g independently at each instance is 0, 1, 2, 3, 4 or 5;
the dotted bond marks the attachment position; and
R 2 is as defined in claim 1 .
9. A compound as claimed in claim 8 , wherein the sum total of the indices g, h and j in the structures of the formula (R 1 -2) to (R 1 -72) is at most 3 in each case.
10. A compound as claimed in claim 3 , wherein the electron transport group of R a and/or R b has independently of each other at least one structure of the formula (E-24) to (E-38)
where the dotted bond marks the attachment position.
11. A compound as claimed in claim 3 , wherein the electron transport group of R a and/or R b has at least one structure of the formula (E-17) to (E-23)
where the dotted bond marks the attachment position and R 1# in the electron-transporting group E are independently of each other selected from the group consisting of H and an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R 2 radicals.
12. A compound as claimed in claim 3 , wherein the hole transport group of R a and/or R b has at least one structure of the formula (L-1) to (L-9)
where the dotted bond marks the attachment position, e is 0, 1 or 2, j is 0, 1, 2 or 3, h is 0, 1, 2, 3 or 4, n is 0 or 1, Ar is an aryl group having 6 to 40 carbon atoms or a heteroaryl group having 3 to 40 carbon atoms which may be substituted by one or more R 1± radicals, and R 1+ is the same or different at each instance and is H, F, Cl, Br, I, B(OR 2 ) 2 , CHO, C(═O)R 2 , CR 2 ═C(R 2 ) 2 , CN, C(═O)OR 2 , C(═O)N(R 2 ) 2 , Si(R 2 ) 3 , N(R 2 ) 2 , NO 2 , P(═O)(R 2 ) 2 , OSO 2 R 2 , OR 2 , S(═O)R 2 , S(═O) 2 R 2 , a straight-chain alkyl, alkoxy or thioalkoxy group having 1 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 R 2 radicals, where one or more nonadjacent CH 2 groups may be replaced by —R 2 C≡CR 2 —, —C≡C—, Si(R 2 ) 2 , Ge(R 2 ) 2 , Sn(R 2 ) 2 , C═O, C═S, C═Se, C═NR 2 , —C(═O)O—, —C(═O)NR 2 —, NR 2 , P(═O)(R 2 ), —O—, —S—, SO or SO 2 and where one or more hydrogen atoms may be replaced by F, Cl, Br, I, CN or NO 2 , or an aromatic or heteroaromatic ring system which has 5 to 40 aromatic ring atoms and may be substituted in each case by one or more R 2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms and may be substituted by one or more R 2 radicals, or a combination of these systems; at the same time, two or more adjacent R 1 substituents together may also form a mono- or polycyclic, aliphatic or aromatic ring system.
13. An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 1 , wherein one or more bonds of the compound to the polymer, oligomer or dendrimer are present.
14. A composition comprising at least one compound as claimed in claim 1 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, matrix materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials and hole blocker materials.
15. A formulation comprising at least one compound as claimed in claim 1 , and at least one solvent.
16. A method comprising providing the compound as claimed in claim 1 , and including the compound in an electronic device as electron blocker material, hole injection material and/or hole transport material.
17. An electronic device comprising at least one compound as claimed in claim 1 .
18. The electronic device as claimed in claim 17 , wherein the electronic device is preferably 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 optical detectors, organic photoreceptors, organic field quench devices, light-emitting electrochemical cells and organic laser diodes.
19. A compound according to claim 1 , selected from the group consisting of