Phenanthroazole compounds as hole transporting materials for electro luminescent devices
The present invention relates to electroluminescent devices, comprising a compound of the formula (I) as a component of the transporting/injecting and/or electron blocking layer. The compounds of formula (I) may function alone, or in combination with dopants to provide improved efficiency, driving voltage and/or lifetime of electroluminescent devices.
1. An electroluminescent (EL) device, comprising
(a) an anode,
(b) a hole transporting/injecting layer,
(c) optionally an electron blocking layer,
(d) a light-emitting layer,
(e) optionally a hole- or exciton-blocking layer,
(f) an electron-transporting layer, and
(g) a cathode,
wherein:
the hole transporting/injecting layer, (b) the electron blocking layer (c), or both layers of (b) and (c), comprises a compound of the formula (I)
R 1 and R 4 are independently of each other hydrogen, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E, interrupted by D, or both, C 1 -C 18 perfluoroalkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy which is substituted by E, interrupted by D, or both, CN, or —CO—R 28 ;
R 2 , R 3 , R 5 and R 6 are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E, interrupted by D, or both, C 1 -C 18 perfluoroalkyl, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy which is substituted by E, interrupted by D, or both, C 7 -C 25 aralkyl, CN, or —CO—R 28 , wherein, optionally, at least one combination of i) R 2 and R 3 and ii) R 5 and R 6 form a group:
R 8 is C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E, interrupted by D, or both, C 1 -C 18 perfluoroalkyl, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, or C 2 -C 20 heteroaryl which is substituted by G,
R 9 is H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E, interrupted by D, or both, C 1 -C 18 perfluoroalkyl, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, or C 2 -C 20 heteroaryl which is substituted by G,
R 105 , R 106 , R 107 , R 108 , R 106′ and R 108′ are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E, interrupted by D, or both, C 1 -C 18 alkoxy, or C 1 -C 18 alkoxy which is substituted by E, interrupted by D, or both;
A 1 , A 2 , A 1′ and A 2′ are independently of each other a group of formula
or A 1 and A 1′ , A 2 and A 2′ , or both A 1 and A 1′ and A 2 and A 2′ , together with the nitrogen atom to which they are bonded form a heteroaromatic ring, or ring system;
R 41 can be the same or different at each occurrence and is Cl, F, CN, N(R 45 ) 2 , a C 1 -C 25 alkyl group, a C 4 -C 18 cycloalkyl group, a C 1 -C 25 alkoxy group, in which one or more carbon atoms which are not adjacent to each other are optionally replaced by —NR 45 —, —O—, —S—, or —C(═O)—O—, and/or wherein one or more hydrogen atoms are optionally replaced by F, a C 6 -C 24 aryl group, or a C 6 -C 24 aryloxy group, wherein one or more carbon atoms are optionally replaced by O, S, or N, and/or which are optionally substituted by one or more non-aromatic groups R 41 , or
two or more groups R 41 form a ring system;
R 45 is H, a C 1 -C 25 alkyl group, a C 4 -C 18 cycloalkyl group, in which one or more carbon atoms which are not adjacent to each other are optionally replaced by —NR 45″ —, —O—, —S—, —C(═O)—O—, or, —O—C(═O)—O—, and/or wherein one or more hydrogen atoms are optionally replaced by F, a C 6 -C 24 aryl group, or a C 6 -C 24 aryloxy group, wherein one or more carbon atoms are optionally replaced by O, S, or N, and/or which are optionally substituted by one or more non-aromatic groups R 41 ;
R 45″ is H, a C 1 -C 25 alkyl group, or a C 4 -C 18 cycloalkyl group;
R 65′ is H, a C 1 -C 25 alkyl group, a C 4 -C 18 cycloalkyl group, in which one or more carbon atoms which are not adjacent to each other are optionally replaced by —O—, or —S—, and/or wherein one or more hydrogen atoms are optionally replaced by F, a C 6 -C 24 aryl group, or a C 6 -C 24 aryloxy group, wherein one or more carbon atoms are optionally replaced by O, S, or N, and/or which are optionally substituted by G;
R 116 , R 117 and R 117′ are independently of each other H, halogen, —CN, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E, interrupted by D, or both, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy which is substituted by E, interrupted by D, or both, C 7 -C 25 aralkyl, —C(═O)—R 127′ , —C(═O)OR 127′ , or —C(═O)NR 127 R 126 , or
substituents R 116 , R 117 and R 117′ , which are adjacent to each other, can form a ring;
R 119 and R 120 are independently of each other C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E, interrupted by D, or both, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy which is substituted by E, interrupted by D, or both, or C 7 -C 25 aralkyl, or
R 119 and R 120 together form a group of formula ═CR 121 R 122 , wherein R 121 and R 122 are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E, interrupted by D, or both, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, or C 2 -C 20 heteroaryl, or C 2 -C 20 heteroaryl which is substituted by G, or
R 119 and R 120 together form a five or six membered ring, optionally substituted by C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E, interrupted by D, or both, C 6 -C 24 aryl, C 6 -C 24 aryl which is substituted by G, C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by G, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy which is substituted by E, interrupted by D, or both, C 7 -C 25 aralkyl, or —C(═O)—R 127′ ; and
R 126 , R 127 and R 127′ are independently of each other C 6 -C 18 aryl, C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy, C 1 -C 18 alkyl, or C 1 -C 18 alkyl which is interrupted by —O—;
D is —CO—, —COO—, —S—, —SO—, —SO 2 —, —O—, —NR 25 —, —SiR 30 R 31 —, —POR 32 —, —CR 23 ═CR 24 —, or —C≡C—;
E is —OR 29 , —SR 29 , —NR 25 R 26 , —COR 28 , —COOR 27 , —CONR 25 R 26 , —CN, or halogen;
G is E, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is interrupted by D, C 1 -C 18 perfluoroalkyl, C 1 -C 18 alkoxy, or C 1 -C 18 alkoxy which is substituted by E, interrupted by D, or both;
R 23 and R 24 are independently of each other C 6 -C 18 aryl, C 6 -C 18 aryl which is substituted by C 1 -C 8 alkyl or C 1 -C 18 alkoxy, C 1 -C 8 alkyl, or C 1 -C 8 alkyl which is interrupted by —O—;
R 25 and R 26 are independently of each other C 6 -C 18 aryl, C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl or C 1 -C 18 alkoxy, C 1 -C 18 alkyl, or C 1 -C 18 alkyl which is interrupted by —O—, or
R 25 and R 26 together form a five or six membered ring;
R 27 and R 28 are independently of each other C 6 -C 18 aryl, C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl or C 1 -C 18 alkoxy, C 1 -C 18 alkyl, or C 1 -C 18 alkyl which is interrupted by —O—;
R 29 is C 6 -C 18 aryl, C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl or C 1 -C 18 alkoxy, C 1 -C 18 alkyl, or C 1 -C 18 alkyl which is interrupted by —O—;
R 30 and R 31 are independently of each other C 1 -C 18 alkyl, C 6 -C 18 aryl, or C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl; and
R 32 is C 1 -C 18 alkyl, C 6 -C 18 aryl, or C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl.
2. The device of claim 1 , wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are hydrogen.
3. The device of claim 1 , wherein:
A 1 , A 1′ , A 2 and A 2′ are independently of each other a group of formula
or A 1 and A 1′ together with the nitrogen atom to which they are bonded form a group of formula
R 116 , R 117 and R 117′ are independently of each other H, or C 1 -C 18 alkyl.
4. The device of claim 1 , wherein:
R 8 is C 1 -C 18 alkyl, C 1 -C 18 alkyl which is interrupted by D, C 1 -C 18 perfluoroalkyl, C 6 -C 18 aryl which may optionally be substituted by C 1 -C 18 alkyl, C 1 -C 18 perfluoroalkyl, C 1 -C 18 alkoxy, or C 1 -C 18 alkoxy which is interrupted by D;
R 9 is H, C 1 -C 18 alkyl, C 1 -C 18 alkyl, which is interrupted by D, C 1 -C 18 perfluoroalkyl, C 6 -C 18 aryl which may optionally be substituted by C 1 -C 18 alkyl, C 1 -C 18 perfluoroalkyl, C 1 -C 18 alkoxy, or C 1 -C 18 alkoxy which is interrupted by D;
D is —O—, —S—, or —NR 25 —; and
R 25 is C 6 -C 18 aryl, C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl or C 1 -C 18 alkoxy, C 1 -C 18 alkyl, or C 1 -C 18 alkyl which is interrupted by —O.
5. The device of claim 1 , wherein:
the compound of formula (I) is a compound of formula (Ia)
A 1 and A 1′ are independently of each other a group of formula
R 116 , R 117 and R 117′ are independently of each other H, or C 1 -C 18 alkyl, or
A 1 and A 1′ together with the nitrogen atom to which they are bonded form a group of formula
R 8 is a group of formula
R 9 is a group of formula
and
R 128 , R 129 , R 130 and R 131 are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkoxy, or C 1 -C 18 perfluoroalkyl.
6. The device of claim 1 , wherein:
the compound of formula (I) is a compound of formula (Ia):
A 1 and A 1′ are independently of each other a group of formula
or A 1 and A 1′ together with the nitrogen atom to which they are bonded form a group of formula
R 116 , R 117 and R 117′ are independently of each other H, or C 1 -C 18 alkyl;
R 8 is a group of formula
R 9 is a group of formula
and
R 128 , R 129 , R 132 and R 133 are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkoxy, or C 1 -C 18 perfluoroalkyl.
7. The device of claim 1 , wherein the compound of formula (I) is a compound of formula
selected from the group consisting of:
Cpd.
A 1
A 1′
R 8
R 9
A-1
A-2
A-3
A-4
A-5
A-6
A-7
A-8
A-9
A-10
A-11
A-12
A-13
A-14
A-15
A-16
A-17
A-18
A-19
A-20
A-21
A-22
A-23
A-24
A-25
A-26
A-27
A-28
A-29
A-30
A-31
A-32
A-33
A-34
A-35
A-36
A-37
A-38
A-39
A-40
A-41
A-42
A-43
A-44
A-45
1)
1)
wherein
8. The device of claim 1 , wherein the hole transporting/injecting layer (b) comprises the compound of formula (I) and a dopant, and
the dopant is at least one selected from the group consisting of titanium oxide (TiO x ), vanadium oxide (VO x ), molybdenium oxide (MoO 3 ), especially MO 3 , tungsten oxide (WO x ), ruthenium oxide (RuO x ), chromium oxide (CrO x ), zirconium oxide (ZrO x ), hafnium oxide (HfO x ) tantalum oxide (TaO x ), silver oxide (AgO x ), manganese oxide (MnO x ), iron tricloride (FeCl 3 ), antimony pentachloride (SbCl 5 ), a metal phthalocyanine compound, dicyano(phthalocyanato(−1)cobalt(III), a oxocarbon-, pseudooxocarbon- or radialene compound, a dicyano(phthalocyanato(−1)ruthenium(III) compound, 2-(6-dicyanomethylene-1,3,4,5,7,8-hexafluoro-6H-naphthalen-2-ylidene)-malononitrile,
2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F 4 -TCNQ),
9. The device of claim 1 , wherein the electron blocking layer (c) comprises the compound of formula (I).
10. The device of claim 1 , wherein:
A 1 and A 1′ , A 2 and A 2′ , or A 1 and A 1′ and A 2 and A 2′ , together with the nitrogen atom to which they are bonded form a heteroaromatic ring system:
m′ is 0, 1, or 2;
m can be the same or different at each occurrence and is 0, 1, 2, or 3;
R 41 can be the same or different at each occurrence and is Cl, F, CN, N(R 45 ) 2 , a C 1 -C 25 alkyl group, a C 4 -C 18 cycloalkyl group, a C 1 -C 25 alkoxy group, in which one or more carbon atoms which are not adjacent to each other are optionally replaced by —NR 45 —, —O—, —S—, or —C(═O)—O—, and/or wherein one or more hydrogen atoms can be replaced by F, a C 6 -C 24 aryl group, or a C 6 -C 24 aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R 41 , or
two or more groups R 41 form a ring system;
R 45 is H, a C 1 -C 25 alkyl group, a C 4 -C 18 cycloalkyl group, in which one or more carbon atoms which are not adjacent to each other could be replaced by —NR 45″ —, —O—, —S—, —C(═O)—O—, or, —O—C(═O)—O—, and/or wherein one or more hydrogen atoms can be replaced by F, a C 6 -C 24 aryl group, or a C 6 -C 24 aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R 41 ; and
R 45″ is H, a C 1 -C 25 alkyl group, or a C 4 -C 18 cycloalkyl group.
11. The device of claim 10 , wherein m is 0, 1 or 2.
12. The device of claim 2 , wherein:
A 1 , A 1′ , A 2 and A 2′ are independently of each other a group of formula
or A 1 and A 1′ together with the nitrogen atom to which they are bonded form a group of formula
R 116 , R 117 and R 117′ are independently of each other H, or C 1 -C 18 alkyl.
13. The device of claim 2 , wherein:
R 8 is C 1 -C 18 alkyl, C 1 -C 18 alkyl which is interrupted by D, C 1 -C 18 perfluoroalkyl, C 1 -C 18 aryl which may optionally be substituted by C 1 -C 18 alkyl, C 1 -C 18 perfluoroalkyl, C 1 -C 18 alkoxy, or C 1 -C 18 alkoxy which is interrupted by D;
R 9 is H, C 1 -C 18 alkyl, C 1 -C 18 alkyl, which is interrupted by D, C 1 -C 18 perfluoroalkyl, C 6 -C 18 aryl which may optionally be substituted by C 1 -C 18 alkyl, C 1 -C 18 perfluoroalkyl, C 1 -C 18 alkoxy, or C 1 -C 18 alkoxy which is interrupted by D;
D is —O—, —S—, or —NR 25 —; and
R 25 is C 6 -C 18 aryl, C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl or C 1 -C 18 alkoxy, C 1 -C 18 alkyl, or C 1 -C 18 alkyl which is interrupted by —O.
14. The device of claim 2 , wherein:
the compound of formula (I) is a compound of formula (Ia)
A 1 and A 1′ are independently of each other a group of formula
R 116 , R 117 and R 117′ are independently of each other H, or C 1 -C 18 alkyl, or
A 1 and A 1′ together with the nitrogen atom to which they are bonded form a group of formula
R 8 is a group of formula
R 9 is a group of formula
and
R 128 , R 129 , R 130 and R 131 are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkoxy, or C 1 -C 18 perfluoroalkyl.
15. The device of claim 2 , wherein:
the compound of formula (I) is a compound of formula (Ia);
A 1 and A 1′ are independently of each other a group of formula
or A 1 and A 1′ together with the nitrogen atom to which they are bonded form a group of formula
R 116 , R 117 and R 117′ are independently of each other H, or C 1 -C 18 alkyl;
R 8 is a group of formula
R 9 is a group of formula
and
R 128 , R 129 , R 132 and R 133 are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkoxy, or C 1 -C 18 perfluoroalkyl.
16. The device of claim 2 , wherein the compound of formula (I) is a compound of formula
selected from the group consisting of:
Cpd.
A 1
A 1′
R 8
R 9
A-1
A-2
A-3
A-4
A-5
A-6
A-7
A-8
A-9
A-10
A-11
A-12
A-13
A-14
A-15
A-16
A-17
A-18
A-19
A-20
A-21
A-22
A-23
A-24
A-25
A-26
A-27
A-28
A-29
A-30
A-31
A-32
A-33
A-34
A-35
A-36
A-37
A-38
A-39
A-40
A-41
A-42
A-43
A-44
A-45
1)
1)
wherein
17. The device of claim 2 , wherein the hole transporting/injecting layer (b) comprises the compound of formula (I) and a dopant, and the dopant is at least one selected from the group consisting of titanium oxide (TiO x ), vanadium oxide (VO x ), molybdenium oxide (MoO 3 ), especially MO 3 , tungsten oxide (WO x ), ruthenium oxide (RuO x ), chromium oxide (CrO x ), zirconium oxide (ZrO x ), hafnium oxide (HfO x ) tantalum oxide (TaO x ), silver oxide (AgO x ), manganese oxide (MnO x ), iron tricloride (FeCl 3 ), antimony pentachloride (SbCl 5 ), a metal phthalocyanine compound, dicyano(phthalocyanato(−1)cobalt(III), a oxocarbon-, pseudooxocarbon- or radialene compound, a dicyano(phthalocyanato(−1)ruthenium(III) compound, 2-(6-dicyanomethylene-1,3,4,5,7,8-hexafluoro-6H-naphthalen-2-ylidene)-malononitrile,
2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F 4 -TCNQ),