4H-imidazo[1,2-a]imidazoles for electronic applications
The present invention relates to compounds of formula a process for their production and their use in electronic devices, especially electroluminescent devices. When used as 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 1 —, or
X 7 is ═N— and X 6 is —NR 1 —,
R 11 , R 12 , R 13 and R 14 are independently of each other H, a C 1 -C 25 alkyl group, which can optionally be substituted by E and or interrupted by D; a C 6 -C 24 aryl group, which can optionally be substituted by G, or a C 2 -C 30 heteroaryl group, which can optionally be substituted by G, and
R 1 is a group of formula -A 1 -(A 2 ) p -(A 3 ) q -(A 4 ) r -R 6 ,
p is 0, or 1, q is 0, or 1, r is 0, or 1,
A 1 , A 2 , A 3 and A 4 are independently of each other a C 6 -C 24 arylene group, which can optionally be substituted by G, or a C 2 -C 30 heteroarylene group, which can optionally be substituted by G; wherein
the groups A 1 , A 2 , A 3 and A 4 may be interrupted by one, or more groups —(SiR 7 R 8 )—;
R 2 , R 3 , R 4 and R 5 are independently of each other H, a C 1 -C 25 alkyl group, which can optionally be substituted by E and or interrupted by D; a C 6 -C 24 aryl group, which can optionally be substituted by G, or a C 2 -C 30 heteroaryl group, which can optionally be substituted by G;
R 6 is H, a group —(SiR 20 R 21 R 22 ), a C 6 -C 24 aryl group, which can optionally be substituted by G, or a C 2 -C 30 heteroaryl group, which can optionally be substituted by G;
R 7 and R 8 are independently of each other a C 1 -C 25 alkyl group, or a C 6 -C 24 aryl group, which can optionally be substituted by G;
R 20 , R 21 and R 22 are independently of each other a C 1 -C 25 alkyl group, or a C 6 -C 24 aryl group, which can optionally be substituted by G;
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 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, which is substituted by F, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is interrupted by O, a C 2 -C 30 heteroaryl group, or a C 2 -C 30 heteroaryl group, which is substituted by F, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is interrupted by O;
R 63 and R 64 are independently of each other C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—;
R 65 and R 66 are independently of each other a C 6 -C 18 aryl group; a C 6 -C 18 aryl which is 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—; 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, which is 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 68 is H; a C 6 -C 18 aryl group; a C 6 -C 18 aryl group, which is 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 69 is a C 6 -C 18 aryl; a C 6 -C 18 aryl, which is 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 independently of each other a C 1 -C 18 alkyl group, a C 6 -C 18 aryl group, or a C 6 -C 18 aryl group, which is 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, which is substituted by C 1 -C 18 alkyl, with the proviso that the following compounds are excluded:
2. The compound according to claim 1 , which is a compound of formula
wherein
R 11 , R 12 , R 13 and R 14 are independently of each other H, a C 1 -C 25 alkyl group, which can optionally be substituted by E and or interrupted by D; a C 6 -C 24 aryl group, which can optionally be substituted by G, or a C 2 -C 30 heteroaryl group, which can optionally be substituted by G, and
E, D, G, R 1 , R 2 , R 3 , R 4 and R 5 are as defined in claim 1 .
3. The compound of formula II according to claim 1 ,
wherein R 2 , R 3 , R 4 , R 5 , R 11 , R 12 , R 13 and R 14 are H and
R 1 is as defined in claim 1 .
4. The compound according to claim 1 , wherein R 1 is a group of formula -A 1 -(A 2 ) p -(A 3 ) q -(A 4 ) r -R 6 , or
wherein
A 1 , A 2 , A 3 and A 4 are independently of each other a group of formula
wherein
m5 is 0, or an integer of 1 to 4,
m2 is 0, or an integer 1 to 3,
X 3 is —O—, —S—, or —NR 15 —,
R 7 and R 8 are a C 1 -C 18 alkyl group,
R 15 is a C 1 -C 18 alkyl group; or a C 1 -C 18 alkyl group, which is interrupted by —O—; a C 6 -C 18 aryl group; a C 6 -C 18 aryl group, which is substituted by one, or more C 1 -C 18 alkyl, or C 1 -C 18 alkoxy groups; a C 2 -C 20 heteroaryl group, or a C 2 -C 20 heteroaryl group, which is substituted by one, or more C 1 -C 18 alkyl groups,
R 41 may be the same, or different in each occurrence and is F, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is 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, and
R 6 , p, q, r, E, D and G are as defined in claim 1 .
5. The compound according to claim 4 , wherein A 1 , A 2 , A 3 and A 4 are independently of each other 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.
6. The compound according to claim 1 , wherein R 6 is a group of formula
or a group —(SiR 20 R 21 R 22 ), wherein
X 6′ is —N═ and X 7′ is —N<, or
X 7′ is ═N— and X 6′ is —N<,
R 2 , R 3 , R 4 , R 5 , R 11 , R 12 , R 13 and R 14 are independently of each other H, a C 1 -C 25 alkyl group, which can optionally be substituted by E and or interrupted by D; a C 6 -C 24 aryl group, which can optionally be substituted by G, or a C 2 -C 30 heteroaryl group, which can optionally be substituted by G,
R 16 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,
R 20 , R 21 and R 22 are independently of each other 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,
R 43 may be the same, or different in each occurrence and is F, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is 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,
m3 is 0, or an integer of 1 to 4, m4 is 0, or an integer of 1 to 3, and
E, D, and G are as defined in claim 1 .
7. The compound according to claim 6 , wherein R 6 is a group of formula
R 16 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.
8. The compound according to claim 1 :
Cpd.
L 1 2)
R 6
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
1)
A-17
1)
A-18
A-19
A-20
Cpd.
L 1 2)
R 6
B-1
B-2
B-3
B-4
B-5
2) The dotted line indicates the bond to the group of formula
9. An electronic device, comprising a compound according to claim 1 .
10. The electronic device according to claim 9 , which is an electroluminescent device.
11. A hole transport layer, or an emitting layer comprising a compound according to claim 1 .
12. An emitting layer comprising a compound according to claim 1 as host material in combination with a phosphorescent emitter.
13. An apparatus selected from the group consisting of stationary visual display units such as visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations, information panels, and mobile visual display units such as visual display units in cellphones, tablet PCs, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains; illumination units; keyboards; items of clothing; furniture; wallpaper, comprising the organic electronic device according to claim 9 .
14. Electrophotographic photoreceptors, photoelectric converters, organic solar cells (organic photovoltaics), switching elements, organic light emitting field effect transistors (OLEFETs), image sensors, dye lasers or electroluminescent devices comprising a compound of formula I according to claim 1 .
15. A process for the preparation of a compound of formula
wherein
R 2 , R 3 , R 4 , R 5 R 11 , R 12 , R 13 and R 14 are H, and R 1 is as defined in claim 1 , comprising
(a) heating a compound of formula
in H 3 PO 4 , polyphosporic acid, CH 3 SO 3 H/P 2 O 5 , CH 3 SO 3 H, or sulfuric acid to obtain a compound of formula
and
(b) reacting the compound of formula XI to a compound of formula II.
16. A compound of the formula
wherein
X 6′ is —N═ and X 7′ is —NR″—, or
X 7′ is ═N— and X 6′ is —NR″—,
R 1′ is a group of formula -A 1 -(A 2 ) p -(A 3 ) q -(A 4 ) r -(R 6′ ) t ,
t is 1, or 2,
p is 0, or 1, u is 0, or 1, r is 0, or 1,
A 1 , A 2 , A 3 and A 4 are independently of each other a C 6 -C 24 arylene group, which can optionally be substituted by G, or a C 2 -C 30 heteroarylene group, which can optionally be substituted by G; wherein
the groups A 1 , A 2 , A 3 and A 4 may be interrupted by one, or more groups —(SiR 7 R 8 )—;
R 2 , R 3 , R 4 and R 5 are independently of each other H, a C 1 -C 25 alkyl group, which can optionally be substituted by E and or interrupted by D; a C 6 -C 24 aryl group, which can optionally be substituted by G, or a C 2 -C 30 heteroaryl group, which can optionally be substituted by G;
R 7 and R 8 are independently of each other a C 1 -C 25 alkyl group, or a C 6 -C 24 aryl group, which can optionally be substituted by G;
X 1 is N, or CR 9 , X 2 is N, or CR 10 ,
R 9 and R 10 are independently of each other H, a C 1 -C 25 alkyl group, which can optionally be substituted by E and or interrupted by D; a C 6 -C 24 aryl group, which can optionally be substituted by G, or a C 2 -C 30 heteroaryl group, which can optionally be substituted by G; or
R 9 and R 10 together form a ring, which can optionally be substituted,
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 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, which is substituted by F, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is interrupted by O, a C 2 -C 30 heteroaryl group, or a C 2 -C 30 heteroaryl group, which is substituted by F, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is interrupted by O;
R 63 and R 64 are independently of each other C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—;
R 65 and R 66 are independently of each other a C 6 -C 18 aryl group; a C 6 -C 18 aryl which is 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—; 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, which is 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 68 is H; a C 6 -C 18 aryl group; a C 6 -C 18 aryl group, which is 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 69 is a C 6 -C 18 aryl; a C 6 -C 18 aryl, which is 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 independently of each other a C 1 -C 18 alkyl group, a C 6 -C 18 aryl group, or a C 6 -C 18 aryl group, which is 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, which is substituted by C 1 -C 18 alkyl,
and R 6′ is Br or I, ZnX 12 ; —SnR 207 R 208 R 209 , wherein R 207 , R 208 and R 209 are identical or different and are H or C 1 -C 6 alkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or unbranched; and X 12 is a halogen atom, —OS(O) 2 CF 3 , —OS(O) 2 -aryl, —OS(O) 2 CH 3 , —B(OH) 2 , —B(OY 1 ) 2 ,
—BF 4 Na, or —BF 4 K, wherein Y 1 is independently in each occurrence a C 1 -C 10 alkyl group and Y 2 is independently in each occurrence a C 2 -C 10 alkylene group, and Y 13 and Y 14 are independently of each other hydrogen, or a C 1 -C 10 alkyl group.
17. The compound according to claim 4 , wherein the group of formula -A 1 -(A 2 ) p -(A 3 ) q -(A 4 ) r - is a group of formula
18. The compound according to claim 6 , wherein R 6 is a group of formula
wherein
R 2 , R 3 , R 4 , R 5 , R 11 , R 12 , R 13 and R 14 are as defined in claim 6 .