4H-imidazo[1,2-a]imidazoles for electronic applications
The present invention relates to compounds of formula (I), a process for their production and their use in electronic devices, especially electroluminescent devices. When used as electron transport and/or host material for phosphorescent emitters in electroluminescent devices, the compounds of formula I may provide improved efficiency, stability, manufacturability, or spectral characteristics of electroluminescent devices.
1. A compound of the formula
wherein:
X 6 is —N═ and X 7 is —NR 6 —; or
X 7 is ═N— and X 6 is —NR 6 —;
R 6 is a group of formula
or
A 1 is a branching unit having three linkage sites;
A 2 and A 3 are each independently a C 6 -C 24 arylen group, optionally substituted by G, or a C 2 -C 30 heteroarylen group, optionally substituted by G; wherein the groups A 1 , A 2 and A 3 may be interrupted by one or more groups —(SiR 7 R 8 )—;
R 1 and R 1′ are each independently H, a C 1 -C 25 alkyl group, optionally substituted by E and/or interrupted by D; a C 6 -C 24 aryl group, optionally substituted by G, or a C 2 -C 30 heteroaryl group, optionally substituted by G;
R 7 and R 8 are each independently a C 1 -C 25 alkyl group, or a C 6 -C 24 aryl group, optionally substituted by G;
L is a single bond or a linking group;
X 1 is N or CR 9 ;
X 2 is N or CR 10 ;
X 3 is N or CR 48 ;
X 4 is N or CR 49 ;
X 5 is N or CR 50 , with the proviso that at least one of X 3 , X 4 and X 5 is N;
R 48 , R 49 , R 50 , R 9 , R 10 , R 9′ and R 10′ are each independently H, a C 1 -C 25 alkyl group, optionally substituted by E and/or interrupted by D; a C 6 -C 24 aryl group, optionally substituted by G, or a C 2 -C 30 heteroaryl group, optionally substituted by G; or
R 9 and R 10 and/or R 9′ and R 10′ together form an optionally substituted ring;
p is 0, 1, or 2; q is 0, 1, or 2;
D is —CO—, —COO—, —S—, —SO—, —SO 2 —, —O—, —NR 65 —, —SiR 70 R 71 —, —POR 72 —, CR 63 ═CR 64 —, or —C≡C—;
E is —OR 69 , —SR 69 , —NR 65 R 66 , —COR 68 , —COOR 67 , —CONR 65 R 66 , —CN, or a halogen;
G is E or a C 1 -C 18 alkyl group, a C 6 -C 24 aryl group, a C 6 -C 24 aryl group substituted by a C 1 -C 18 alkyl; a C 2 -C 30 heteroaryl group, or a C 2 -C 30 heteroaryl group substituted by a C 1 -C 18 alkyl;
R 63 and R 64 are each independently H, a C 6 -C 18 aryl; a C 6 -C 18 aryl substituted by a C 1 -C 18 alkyl, a C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or a C 1 -C 18 alkyl which is interrupted by —O—;
R 65 and R 66 are each independently a C 6 -C 18 aryl group; a C 6 -C 18 aryl substituted by a C 1 -C 18 alkyl, or a C 1 -C 18 alkoxy; a C 1 -C 18 alkyl group; or a C 1 -C 18 alkyl group, which is interrupted by —O—; or
R 65 and R 66 together form a five or six membered ring;
R 67 is a C 6 -C 18 aryl group; a C 6 -C 18 aryl group, substituted by a C 1 -C 18 alkyl, or a C 1 -C 18 alkoxy; a C 1 -C 18 alkyl group; or a C 1 -C 18 alkyl group, which is interrupted by —O—,
R 68 is H; a C 6 -C 18 aryl group; a C 6 -C 18 aryl group, substituted by a C 1 -C 18 alkyl, or a C 1 -C 18 alkoxy; a C 1 -C 18 alkyl group; or a C 1 -C 18 alkyl group, which is interrupted by —O—;
R 69 is a C 6 -C 18 aryl; a C 6 -C 18 aryl, substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; a C 1 -C 18 alkyl group; or a C 1 -C 18 alkyl group, which is interrupted by —O—;
R 70 and R 71 are each independently a C 1 -C 18 alkyl group, a C 6 -C 18 aryl group, or a C 6 -C 18 aryl group, substituted by C 1 -C 18 alkyl; and
R 72 is a C 1 -C 18 alkyl group, a C 6 -C 18 aryl group, or a C 6 -C 18 aryl group, substituted by a C 1 -C 18 alkyl, with the proviso that the following compound is excluded:
2. The compound of claim 1 , which is a compound of formula
wherein:
R 2 , R 3 , R 4 and R 5 are each independently H, a C 1 -C 25 alkyl group, optionally substituted by E and/or interrupted by D; a C 6-24 aryl group, optionally substituted by G, or a C 2 -C 30 heteroaryl group, optionally substituted by G.
3. The compound of claim 1 , which is a compound of formula
wherein
X 6 is —N═ and X 7 is —NR 6 —; or
X 7 is ═N— and X 6 is —NR 6 —;
R 6 is a group of formula
wherein A 1 is a group of formula
A 2 and A 3 are a group of formula
R 11 , R 12 , R 13 and R 14 are each independently H, a C 1 -C 25 alkyl group, optionally substituted by E and/or interrupted by D; a C 6 -C 24 aryl group, optionally substituted by G, or a C 2 -C 30 heteroaryl group, optionally substituted by G; and
R 2 , R 3 , R 4 and R 5 are each independently H, a C 1 -C 25 alkyl group, optionally substituted by E and/or interrupted by D; a C 6-24 aryl group, optionally substituted by G, or a C 2 -C 30 heteroaryl group, optionally substituted by G.
4. The compound of claim 3 , wherein R 2 , R 3 , R 4 , R 5 , R 11 , R 12 , R 13 and R 14 are H.
5. The compound of claim 1 , wherein R 1 and R 1′ are each independently a group of formula
or a group —(SiR 20 R 21 R 22 ), wherein
X 8 is —N═ and X 9 is >N-L-;
X 9 is ═N— and X 8 is >N-L-;
R 2 , R 3 , R 4 , R 5 , R 11 , R 12 , R 13 and R 14 are each independently H, a C 1 -C 25 alkyl group, optionally substituted by E and/or interrupted by D; a C 6 -C 24 aryl group, optionally substituted by G, or a C 2 -C 30 heteroaryl group, optionally substituted by G;
R 16 is a C 6 -C 18 aryl group; or a C 6 -C 18 aryl group, substituted by one, or more C 1 -C 18 alkyl groups;
R 20 , R 21 and R 22 are each independently a C 6 -C 18 aryl group; or a C 6 -C 18 aryl group, substituted by one or more C 1 -C 18 alkyl groups;
R 43 may be the same, or different in each occurrence and is F, C 1 -C 18 alkyl, C 1 -C 18 alkyl substituted by E and/or interrupted by D, 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 91 , R 92 , R 93 , R 94 and R 95 are each independently H, a C 1 -C 25 alkyl group, optionally substituted by E and/or interrupted by D;
m3 is 0 or an integer of 1 to 4;
m4 is 0 or an integer of 1 to 3.
6. The compound of claim 5 , wherein R 1 and R 1′ are independently a group of formula
wherein R 16 is a C 6 -C 18 aryl group; or a C 6 -C 18 aryl group, substituted by one or more C 1 -C 18 alkyl groups.
7. The compound of claim 1 , wherein L is a single bond, a group of formula -(A 4 ) r -(A 5 ) s -A 6 -, or
wherein
A 4 , A 5 and A 6 are each independently a group of formula
wherein
R 41 may be the same, or different in each occurrence and is F, C 1 -C 18 alkyl, C 1 -C 18 alkyl substituted by E and/or interrupted by D, C 6 -C 24 aryl, C 6 -C 24 aryl substituted by G, C 2 -C 20 heteroaryl, or C 2 -C 20 heteroaryl substituted by G,
m1 is 0, or an integer of 1 to 4,
m2 is 0, or an integer 1 to 3,
r is 0, or 1; s is 0, or 1;
X 13 is —O—, —S—, or —NR 15 —,
R 15 is a C 1 -C 18 alkyl group; or a C 1 -C 18 alkyl group, interrupted by —O—; a C 6 -C 18 aryl group; a C 6 -C 18 aryl group, substituted by one or more C 1 -C 18 alkyl groups, or C 1 -C 18 alkoxy groups; a C 2 -C 20 heteroaryl group, or a C 2 -C 20 heteroaryl group, substituted by one or more C 1 -C 18 alkyl groups,
R 7 and R 8 are a C 1 -C 18 alkyl group.
8. The compound of claim 7 , wherein A 4 , A 5 and A 6 are each independently a group of formula
wherein
R 15 is a C 6 -C 18 aryl group; or a C 6 -C 18 aryl group, which is substituted by one, or more C 1 -C 18 alkyl groups.
9. The compound of claim 1 , having a formula:
wherein L, R 1 and R 1′ are defined by any one of the compounds A-1-A-18:
Cpd.
L 3)
R 1
R 1′
A-1
A-2
A-3
A-4
A-5
A-6
A-7
1)
A-8
1)
A-9
single bond
A-10
single bond
A-11
single bond
2)
A-12
single bond
2)
2)
A-13
A-14
A-15
single bond
A-16
A-17
A-18
single bond
or having a formula:
wherein L, R 1 and R 1′ are defined by any one of the compounds B-1-B-18:
Cpd.
L 3)
R 1
R 1′
B-1
B-2
B-3
B-4
B-5
B-6
B-7
1)
B-8
1)
B-9
single bond
B-10
single bond
B-11
single bond
2)
B-12
single bond
2)
2)
B-13
B-14
B-15
single bond
B-16
B-17
B-18
single bond
or having a formula:
wherein L, R 1 , and R 1′ are defined by any one of the compounds C-1-C-18:
Cpd.
L 3)
R 1
R 1′
C-1
C-2
C-3
C-4
C-5
C-6
C-7
1)
C-8
1)
C-9
single bond
C-10
single bond
C-11
single bond
2)
C-12
single bond
2)
2)
C-13
C-14
C-15
single bond
C-16
C-17
C-18
single bond
or having a formula:
wherein L, R 1 , and R 1′ are defined by any one of the compounds D-1-D-19:
Cpd.
L 3)
R 1
R 1′
D-1
D-2
D-3
D-4
D-5
D-6
D-7
1)
D-8
1)
D-9
single bond
D-10
single bond
D-11
single bond
2)
D-12
single bond
2)
2)
D-13
single bond
H
2)
D-14
D-15
D-16
single bond
D-17
D-18
D-19
single bond
or having a formula:
wherein Z 1 , Z 2 , and A 2 are defined by any one of the compounds E-1-E-6:
Cpd.
Z 1
Z 2
A 2
E-1
E-2
E-3
E-4
E-5
E-6
10. An electronic device, comprising the compound of claim 1 .
11. The electronic device of claim 10 , wherein the electronic device is an electroluminescent device.
12. An electron transport layer, a hole/exciton blocking layer, or an emitting layer comprising the compound of claim 1 .
13. An emitting layer, comprising a compound of claim 1 as a host material in combination with a phosphorescent emitter.
14. An apparatus selected from the group consisting of a stationary visual display unit, a mobile visual display unit, an illumination unit, a keyboard, an item of clothing, a furniture, and a wallpaper, comprising the electronic device of claim 10 .
15. An electrophotographic photoreceptor, a photoelectric converter, an organic solar cell, a switching element, an organic light emitting field effect transistor, an image sensor, a dye laser or an electroluminescent device comprising the compound of claim 1 .