4H-Imidazo[1,2-a]imidazoles for Electronic Applications

Abstract

The present invention relates to compounds of formula

##STR00001##

a process for their production and their use in electronic devices, especially electroluminescent devices. When used as host material for phasphorescent emitters in electroluminescent devices, the compounds of formula I may provide improved efficiency, stability, manufacturability, or spectral characteristics of electroluminescent devices.

Claims

1. A compound of the formula (I) ##STR02055## wherein X.sup.6 is —N═ and X.sup.7 is —NR.sup.1—, or X.sup.7 is ═N and X.sup.6 is —NR.sup.1—, R.sup.1 is a group of formula -A.sup.1-(A.sup.2).sub.p-(A.sup.3).sub.q-(A.sup.4).sub.r-R.sup.6, p is 0, or 1, q is 0, or 1, r is 0, or 1, A.sup.1, A.sup.2, A.sup.3 and A.sup.4 are independently of each other a C.sub.6-C.sub.24 arylene group, which can optionally be substituted by G, or a C.sub.2-C.sub.30 heteroarylene group, which can optionally be substituted by G; wherein the groups A.sup.1, A.sup.2, A.sup.3 and A.sup.4 may be interrupted by one, or more groups —(SiR.sup.7R.sup.8)—; R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are independently of each other H, a C.sub.1-C.sub.25 alkyl group, which can optionally be substituted by E and or interrupted by D; a C.sub.6-C.sub.24aryl group, which can optionally be substituted by G, or a C.sub.2-C.sub.30heteroaryl group, which can optionally be substituted by G; R.sup.6 is H, a group (SiR.sup.20R.sup.21R.sup.22), a C.sub.6-C.sub.24aryl group, which can optionally be substituted by G, or a C.sub.2-C.sub.30heteroaryl group, which can optionally be substituted by G; R.sup.7 and R.sup.8 are independently of each other a C.sub.1-C.sub.25alkyl group, or a C.sub.6-C.sub.24aryl group, which can optionally be substituted by G; X.sup.1 is N, or CR.sup.9, X.sup.2 is N, or CR.sup.10, R.sup.9 and R.sup.10 are independently of each other H, a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E and or interrupted by D; a C.sub.6-C.sub.24aryl group, which can optionally be substituted by G, or a C.sub.2-C.sub.30heteroaryl group, which can optionally be substituted by G; R.sup.9 and R.sup.10 optionally together form a ring, which can optionally be substituted, R.sup.20, R.sup.21 and R.sup.22 are independently of each other a C.sub.1-C.sub.25alkyl group, or a C.sub.6-C.sub.24aryl group, which can optionally be substituted by G; D is —CO—, —COO—, —S—, —SO—, —SO.sub.2—, —O—, —NR.sup.65—, —SiR.sup.70R.sup.71—, —POR.sup.72—, —CR.sup.63═CR.sup.64—, or —C≡C—, E is —OR.sup.69, —SR.sup.69, —NR.sup.65R.sup.66, —COR.sup.68, —COOR.sup.67, —CONR.sup.65R.sup.66, —CN, or halogen, G is E, or a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.24aryl group, a C.sub.6-C.sub.24aryl group, which is substituted by F, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is interrupted by —O—, a C.sub.2-C.sub.30heteroaryl group, or a C.sub.2-C.sub.30heteroaryl group, which is substituted by F, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is interrupted by —O—; R.sup.63 and R.sup.64 are independently of each other C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by —O—; R.sup.65 and R.sup.66 are independently of each other a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.65 and R.sup.66 optionally together form a five or six membered ring, R.sup.67 is a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—, R.sup.68 is H; a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—, R.sup.69 is a C.sub.6-C.sub.18aryl; a C.sub.6-C.sub.18aryl, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O— R.sup.70 and R.sup.71 are independently of each other a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group, or a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl, and R.sup.72 is a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group, or a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl, with the proviso that the following compounds are excluded: ##STR02056## ##STR02057##

2. The compound according to claim 1, which is a compound of formula ##STR02058## wherein X.sup.6 is —N═ and X.sup.7 is —NR.sup.1—, or X.sup.7 is ═N— and X.sup.6 is —NR.sup.1—, R.sup.11, R.sup.12, R.sup.13 and R.sup.14 are independently of each other H, a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E and or interrupted by D; a C.sub.6-C.sub.24aryl group, which can optionally be substituted by G, or a C.sub.2-C.sub.30heteroaryl group, which can optionally be substituted by G.

3. The compound of formula II according to claim 2, wherein R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.11, R.sup.12, R.sup.13 and R.sup.14 are H.

4. The compound according to claim 1, wherein R.sup.1 is a group of formula -A.sup.1-(A.sup.2).sub.p-(A.sup.3).sub.q-(A.sup.4).sub.r-R.sup.6, or ##STR02059## wherein A.sup.1, A.sup.2, A.sup.3 and A.sup.4 are independently of each other a group of formula ##STR02060## wherein m5 is 0, or an integer of 1 to 4, m2 is 0, or an integer 1 to 3, X.sup.3 is —O—, —S—, or —NR.sup.15—, R.sup.7 and R.sup.8 are a C.sub.1-C.sub.18alkyl group, R.sup.15 is a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by one, or more C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy groups; a C.sub.2-C.sub.20heteroaryl group, or a C.sub.2-C.sub.20heteroaryl group, which is substituted by one, or more C.sub.1-C.sub.18alkyl groups, R.sup.41may be the same, or different in each occurrence and is F, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is substituted by E and/or interrupted by D, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl which is substituted by G, C.sub.2-C.sub.20heteroaryl, or C.sub.2-C.sub.20heteroaryl which is substituted by G.

5. The compound according to claim 4, wherein A.sup.1, A.sup.2, A.sup.3 and A.sup.4 are independently of each other a group of formula ##STR02061## wherein R.sup.15 is a C.sub.6-C.sub.18aryl group; or a C.sub.6-C.sub.18aryl group, which is substituted by one, or more C.sub.1-C.sub.18alkyl groups.

6. The compound according to claim 1, wherein R.sup.6 is a group of formula ##STR02062## or a group —(SiR.sup.20R.sup.21R.sup.22), wherein X.sup.6′ is N═ and X.sup.7′ is —N<, or X.sup.7′ is ═N— and X.sup.6′ is —N<, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.11, R.sup.12, R.sup.13 and R.sup.14 are independently of each other H, a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E and or interrupted by D; a C.sub.6-C.sub.24aryl group, which can optionally be substituted by G, or a C.sub.2-C.sub.30heteroaryl group, which can optionally be substituted by G, R.sup.16 is a C.sub.6-C.sub.18aryl group; or a C.sub.6-C.sub.18aryl group, which is substituted by one, or more C.sub.1-C.sub.18alkyl groups. R.sup.20, R.sup.21 and R.sup.22 are independently of each other a C.sub.6-C.sub.18aryl group; or a C.sub.6-C.sub.18aryl group, which is substituted by one, or more C.sub.1-C.sub.18alkyl groups, R.sup.43 may be the same, or different in each occurrence and is F, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is substituted by E and/or interrupted by D, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl which is substituted by G, C.sub.2-C.sub.20heteroaryl, or C.sub.2-C.sub.20heteroaryl 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.

7. The compound according to claim 6, wherein R.sup.6 is a group of formula ##STR02063## R.sup.16 is a C.sub.6-C.sub.18aryl group; or a C.sub.6-C.sub.18aryl group, which is substituted by one, or more C.sub.1-C.sub.18alkyl groups.

8. The compound according to claim 1: TABLE-US-00017 Cpd. L.sup.1 2) R.sup.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 .sup.1) A-17 .sup.1) A-18 A-19 A-20 TABLE-US-00018 Cpd. L.sup.1 2) R.sup.6 B-1 B-2 B-3 B-4 B-5 .sup.2)The dotted line indicates the bond to the group of formula

9. The compound according to claim 1, which is a compound of formula ##STR02116## wherein R.sup.1 is a group of formula -A.sup.1-(A.sup.2).sub.p-(A.sup.3).sub.q-(A.sup.4).sub.r-R.sup.6, or ##STR02117## A.sup.1, A.sup.2, A.sup.3 and A.sup.4 are independently of each other a group of formula ##STR02118## wherein m5 is 0, or an integer of 1 to 4, m2 is 0, or an integer 1 to 3, X.sup.3 is —O—, —S—, or —NR.sup.15—, R.sup.7 and R.sup.8 are a C.sub.1-C.sub.18alkyl group, R.sup.15 is a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by one, or more C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy groups; a C.sub.2-C.sub.20heteroaryl group, or a C.sub.2-C.sub.20heteroaryl group, which is substituted by one, or more C.sub.1-C.sub.18alkyl groups, R.sup.41may be the same, or different in each occurrence and is F, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is substituted by E and/or interrupted by D, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl which is substituted by G, C.sub.2-C.sub.20heteroaryl, or C.sub.2-C.sub.20heteroaryl which is substituted by G, R.sup.6 is a group of formula ##STR02119## R.sup.43 may be the same, or different in each occurrence and is F, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is substituted by E and/or interrupted by D, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl which is substituted by G, C.sub.2-C.sub.20heteroaryl, or C.sub.2-C.sub.20heteroaryl which is substituted by G, R.sup.11, R.sup.12, R.sup.13 and R.sup.14 are independently of each other H, a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E and or interrupted by D; a C.sub.6-C.sub.24aryl group, which can optionally be substituted by G, or a C.sub.2-C.sub.30heteroaryl group, which can optionally be substituted by G; m3 is 0, or an integer of 1 to 4; or R.sup.1 is a group of formula -A.sup.1-(A.sup.2).sub.p-(A.sup.3).sub.q-(A.sup.4).sub.r-R.sup.6, wherein A.sup.1, A.sup.2, A.sup.3 and A.sup.4 are independently of each other a group of formula ##STR02120## R.sup.6 is a group of formula ##STR02121##

10. An electronic device, comprising a compound according to claim 1.

11. The electronic device according to claim 10, which is an electroluminescent device.

12. A hole transport layer, or an emitting layer comprising a compound according to claim 1.

13. The emitting layer according to claim 12, comprising a compound according to claim 1 as host material in combination with a phosphorescent emitter.

14. 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 10.

15. 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 comprise a compound of formula I according to claim 1.

16. A process for the preparation of a compound of formula ##STR02122## wherein R.sup.2, R.sup.3, R.sup.4, R.sup.5R.sup.11, R.sup.12, R.sup.13 and R.sup.14 are H, and R.sup.1 is as defined in claim 1, comprising (a) heating a compound of formula ##STR02123## in H.sub.3PO.sub.4, polyphosphoric acid, CH.sub.3SO.sub.3H/P.sub.2O.sub.5, CH.sub.3SO.sub.3H, or sulfuric acid to obtain a compound of formula ##STR02124## and (b) reacting the compound of formula XI to a compound of formula II.

17. A compound of the formula ##STR02125## wherein X.sup.6′ is N═ and X.sup.7′ is —NR.sup.1′—, or X.sup.7′ is ═N— and X.sup.6′ is —NR.sup.1′—, X.sup.1 is N or CR.sup.9, X.sup.2 is N or CR.sup.10, R.sup.9 and R.sup.10 are independently of each other H, a C.sub.1-C.sub.25 alkyl group, which can optionally be substituted by E and or interrupted by D: a C.sub.6-C.sub.24 aryl group, which can optionally be substituted by G, or a C.sub.2-C.sub.30 heteroaryl group, which can optionally be substituted by G; R.sup.9 and R.sup.10 optionally together form a ring, which can optionally be substituted, R.sup.1′ is a group of formula -A.sup.1-(A.sup.2).sub.p-(A.sup.3).sub.q-(A.sup.4).sub.r-(R.sup.6′).sub.t, t is 1, or 2, p is 0, or 1, q is 0, or 1, r is 0, or 1, A.sup.1, A.sup.2, A.sup.3 and A.sup.4 are independently of each other a C.sub.6-C.sub.24 arylene group, which can optionally be substituted by G, or a C.sub.2-C.sub.30 heteroarylene group, which can optionally be substituted by G: wherein the groups A.sup.1, A.sup.2, A.sup.3 and A.sup.4 may be interrupted by one, or more groups —(SiR.sup.7R.sup.8)—; R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are independently of each other H, a C.sub.1-C.sub.25 alkyl group, which can optionally be substituted by E and or interrupted by D; a C.sub.6-C.sub.24aryl group, which can optionally be substituted by G, or a C.sub.2-C.sub.30heteroaryl group, which can optionally be substituted by G; R.sup.6′ is halogen, ZnX.sup.12; —SnR.sup.207R.sup.208R.sup.209, wherein R.sup.207, R.sup.208 and R.sup.209 are identical or different and are H or C.sub.1-C.sub.6alkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or unbranched; and X.sup.12 is a halogen atom, —OS(O).sub.2CF.sub.3, —OS(O).sub.2-aryl, —OS(O).sub.2CH.sub.3, —B(OH).sub.2, —B(OY.sup.1).sub.2, ##STR02126## —BF.sub.4Na, or —BF.sub.4K, wherein Y.sup.1 is independently in each occurrence a C.sub.1-C.sub.10alkyl group and Y.sup.2 is independently in each occurrence a C.sub.2-C.sub.10alkylene group, and Y.sup.13 and Y.sup.14 are independently of each other hydrogen, or a C.sub.1-C.sub.10alkyl group; D is —CO—, —COO—, —S—, —SO—, —SO.sub.2—, —O—, —NR.sup.65, —SiR.sup.70R.sup.71—, —POR.sup.72—, —CR.sup.63═CR.sup.64—, or —C≡C—, E is —OR.sup.69, —SR.sup.69, —NR.sup.65R.sup.66, —COR.sup.68, —COOR.sup.67, —CONR.sup.65R.sup.66, —CN, or halogen, G is E, or a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.24aryl group, a C.sub.6-C.sub.24aryl group, which is substituted by F, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is interrupted by —O—, a C.sub.2-C.sub.30heteroaryl group, or a C.sub.2-C.sub.30heteroaryl group, which is substituted by F, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is interrupted by —O—; R.sup.63 and R.sup.64 are independently of each other C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy: C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by —O—; R.sup.65 and R.sup.66 are independently of each other a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy: a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—; R.sup.65 and R.sup.66 optionally together form a five or six membered ring, R.sup.67 is a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—, R.sup.68 is H; a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O—, R.sup.69 is a C.sub.6-C.sub.18aryl: a C.sub.6-C.sub.18aryl, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by —O— R.sup.70 and R.sup.71 are independently of each other a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group, or a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl, and R.sup.72 is a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group, or a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl.

Description

EXAMPLES

Example 1

[0315] ##STR01986##

[0316] a) 16.4 ml (27.9 mmol) t-butyl-lithium in pentane are added to a solution of 5.00 g (12.1 mmol) 9-(8-bromodibenzofuran-2-yl)carbazole, the synthesis of which is described in WO2010079051, in 30 ml water free tetrahydrofurane (THF) at −78° C. under argon. After 15 minutes 2.93 g (15.8 mmol) 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane are slowly added. The reaction mixture is stirred for 3 h at −78° C. under argon poured into water and the water phase is extracted with diethyl ether. The organic phase is dried with magnesium sulfate and the solvent is removed. Crystallization from ether results in 2.57 g of compound 1 (yield: 46%).

[0317] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.50 (s, 1H), 8.18-8.23 (m, 3H), 8.05 (dd, J=8.3 Hz, J=1.3 Hz, 1H), 7.80-7.82 (m, 1H), 7.64-7.70 (m, 2H), 7.43-7.49 (m, 4H), 7.28-7.37 (m, 2H), 1.43 (s, 12H).

##STR01987##

[0318] b) 11.3 g (50.0 mmol) 3-(2-Aminophenyl)-1H-benzimidazol-2-one are added to 50 g polyphosphoric acid at 180° C. The reaction mixture is stirred at 220° C. for 3 h under nitrogen and poured into water. The product is filtered off and washed with water and methanol. 50 ml 30% sodium hydroxide solution are added to a suspension of the product in 200 ml THF. The mixture is stirred for 30 minutes and the organic phase is separated, dried with magnesium sulfate and the solvent is distilled off. 9.26 g of compound 2 are obtained (yield: 89%).

[0319] .sup.1H NMR (400 MHz, DMSO-d6): δ 7.88 (d, J=7.7 Hz, 2H), 7.39 (d, J=8.0 Hz, 2H), 7.12-7.16 (m, 2H), 6.97-7.01 (m, 2H).

[0320] The synthesis of 5H-benzimidazo[1,2-a]benzimidazole and 3-(2-aminophenyl)-1H-benzimidazol-2-one is described in Bull. Soc. Chem. Belg. 96 (1987) 787.

##STR01988##

[0321] c) 5.00 g (13.4 mmol) 2-bromo-8-iodo-dibenzofuran, the synthesis of which is described in EP1885818, 8.74 g (26.8 mmol) caesium carbonate, 255 mg (1.34 mmol) copper(I) iodide and 309 mg (2.68 mmol) L-proline are added to 2.78 g (13.4 mmol) 5H-benzimidazo[1,2-a]benzimidazole in 75 ml dimethylformamide under nitrogen. The reaction mixture is heated for 19 h at 150° C. and filtered on Hyflo Super Cel® medium, Fluka 56678, CAS [91053-39-3] with THF. The organic phase is washed with water. The solvent is distilled off. Column chromatography on silica gel with toluene/ethyl acetate 19/1 results in compound 3 (yield: 2.29 g (37.7%)).

[0322] .sup.1H NMR (400 MHz, THF-d8): S 8.66 (s, 1H), 8.41 (s, 1H), 8-01-8-16 (m, 3H), 7.89 (d, J=8.8 Hz, 1H), 7.63-7.75 (m, 4H), 7.25-7.49 (m, 4H).

##STR01989##

[0323] d) 1.98 g (3.41 mmol) of compound 1 and 4.02 g (16.6 mmol) potassium phosphate tribasic monohydrate, 15 ml dioxane, 60 ml toluene and 12 ml water are added to 1.50 g (3.32 mmol) of the compound 3. The mixture is degassed with argon. 81 mg (0.199 mmol) 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos) and 74 mg (0.033 mmol) palladium(II) acetate are added. The reaction mixture is degassed with argon and is stirred for 4.5 h at 100° C. under argon. 40 ml of a 1% sodium cyanide solution are added and the reaction mixture is refluxed for 1 h. Dichloromethane is added, the organic phase is washed with water and dried with magnesium sulfate. Column chromatography on silica gel with toluene and then toluene/ethyl acetate 9/1 results in compound A-1 (yield: 1.42 g (61%)). .sup.1H NMR (400 MHz, THF-d8): δ 8.71 (s, 1H), 8.54-8.58 (m, 2H), 8.41 (s, 1H), 8.20 (d, J=7.8 Hz, 2H), 7.62-8.11 (m, 12H), 7.26-7.31 (m, 10H).

Example 2

[0324] The synthesis of 4H-imidazo[1,2-a]benzimidazole is described in ARKIVOC 2002 (v) 48-61.

##STR01990##

[0325] a) 8.02 g (51.0 mmol) 4H-imidazo[1,2-a]benzimidazole, 15.9 g (56.1 mmol) 1-bromo-3-iodo-benzene, 33.2 g (102 mmol) caesium carbonate, 1.94 g (10.2 mol) copper (1) iodide and 2.35 g (20.4 mol) L-proline in 200 ml dimethyl sulfoxide (DMSO) are stirred for 24 h at 100° C. The solids are filtered off and washed with dichloromethane. The organic phase is washed with water and dried with magnesium sulfate. The solvent is distilled off. Column chromatography with toluene and then toluene/ethyl acetate (20/1) results in a product mixture (3.89 g (24%) isomer A and 4.46 g (28%) isomer B). Separation of the two isomers is achieved by gradient column chromatography with toluene/ethyl acetate (toluene 100%, toluene/ethyl acetate 95/5, toluene/ethyl acetate 90/10 and ethylacetate 100%).

##STR01991##

[0326] .sup.1H NMR (400 MHz, THF-d8): δ 8.54-8.56 (m, 1H), 8.33 (dd, J=7.8 Hz, J=1.4 Hz, 1H), 7.80 (d, J=2.8 Hz, 1H), 7.76 (d, J=2.8 Hz, 1H), 7.79 (d, J=8.6 Hz, 2H), 7.39-7.46 (m, 2H), 7.20-7.29 (m, 1H), 7.12-7.16 (in, 1H).

##STR01992##

[0327] .sup.1H NMR (400 MHz, THF-d8): δ 8.23 (s, 1H), 7.95-7.97 (m, 1H), 7.70-7.74 (m, 2H), 7.56 (s, 1H), 7.45-7.53 (m, 2H), 7.24-7.33 (m, 2H), 7.17 (s, 1H).

[0328] b) The synthesis of compound C-1 is carried out in analogy to the synthesis of compound A-1.

##STR01993##

[0329] .sup.1H NMR (400 MHz, THF-d8): 8.63 (s, 1H), 8.52 (s, 1H), 8.42 (s, 1H), 8.32-8.35 (m, 1H), 8.20-8.22 (m, 2H), 7.59-8.02 (m, 10H), 7.40-7.47 (m, 4H), 7.09-7.20 (m, 4H).

[0330] c) The synthesis of the product of Example 2c) is carried out in analogy to the synthesis of compound A-1.

##STR01994##

[0331] .sup.1H NMR (400 MHz, THF-d8): δ=8.51 (d, J=1.7 Hz, 1H), 8.41 (d, J=2.1 Hz, 1H), 8.37-8.39 (m, 1H), 8.21 (s, 1H), 8.19 (s, 1H), 7.98 (dd, J=8.6 Hz, J=1.9 Hz, 1H), 7.91-7.94 (m, 2H), 7.65-7.82 (m, 6H), 7.57 (d, J=1.5 Hz, 1H), 7.37-7.44 (m, 4H), 7.24-7.34 (m, 4H), 7.12 (d, J=1.5 Hz, 1H).

Application Example 1—Mixed-Matrix

[0332] The ITO substrate used as the anode is first cleaned with commercial detergents for LCD production (Deconex® 20NS, and 25ORGAN-ACID® neutralizing agent) and then in an acetone/isopropanol mixture in an ultrasound bath. To eliminate any possible organic residues, the substrate is exposed to a continuous ozone flow in an ozone oven for further 25 minutes. This treatment also improves the hole injection properties of the ITO. Then Plexcore® OC AJ20-1000 (commercially available from Plextronics Inc.) is spin-coated and dried to form a hole injection layer (˜40 nm).

[0333] Thereafter, the organic materials specified below are applied by vapor deposition to the clean substrate at a rate of approx. 0.5-5 nm/min at about 10-7-10-9 mbar. As a hole transport and exciton blocker,

##STR01995##

(for preparation, see Ir complex (7) in the application WO2005/019373) is applied to the substrate with a thickness of 20 nm, wherein the first 10 nm are doped with MoO.sub.x (˜10%) to improve the conductivity.

[0334] Subsequently, a mixture of 30% by weight of emitter compound,

##STR01996##

8% by weight of compound Ir(dpbic).sub.3 and 62% by weight of compound

##STR01997##

is applied by vapor deposition in a thickness of 30 nm.

[0335] Subsequently, the material BAlq

##STR01998##

is applied by vapour deposition with a thickness of 5 nm as blocker.

[0336] Next, a Cs.sub.2CO.sub.3 doped BCP

##STR01999##

layer is applied as electron transport layer by vapor deposition in a thickness of 20 nm and finally a 100 nm-thick Al electrode completes the device.

[0337] All fabricated parts are sealed with a glass lid and a getter in an inert nitrogen atmosphere.

Application Example 2—Single-Matrix

[0338] Production and construction of an OLED as in the application example 1, except the emission-layer consists only of 30% by weight of compound

##STR02000##

and 70% by weight of compound

##STR02001##

i.e. does not comprise compound Ir(dpbic).sub.3.

[0339] To characterize the OLED, electroluminescence spectra are recorded at various currents and voltages. In addition, the current-voltage characteristic is measured in combination with the light output emitted. The light output can be converted to photometric parameters by calibration with a photometer. To determine the lifetime, the OLED is operated at a constant current density and the decrease in the light output is recorded. The lifetime is defined as that time which lapses until the luminance decreases to half of the initial luminance.

TABLE-US-00012 Voltage EQE.sup.1) Lifetime @ 300 @ 300 @ 4000 nits nits nits EML [V] [%] [h] CIE Appl. Ex. 1 Mixed-Matrix 3.8 V 14.7% 125 h 0.17/0.33 Appl. Ex. 2 Single-Matrix 3.6 V 14.2%  65 h 0.17/0.34 .sup.1) External quantum efficiency (EQE) is # of generated photons escaped from a substance or a device/# of electrons flowing through it.

Example 3

[0340] ##STR02002##

[0341] 3.30 g (10 mmol) 1,3-diiodobenzene, 13.0 g (40.0 mmol) caesium carbonate, 1.90 g (1.00 mmol) copper(I) iodide and 2.30 g (20.0 mmol) L-proline are added to 4.56 g (22.0 mmol) mmol) 5H-benzimidazo[1,2-a]benzimidazole in 100 ml dimethylsulfoxide (DMSO) under nitrogen. The reaction mixture is stirred for 5 h at 100° C. The reaction mixture is poured into water and the product is filtered off. The product is two times crystallized form toluene. Yield 1.6 g (48%). MS (APCl(pos): m/z=489 (M.sup.+1).

[0342] .sup.1H NMR (400 MHz, THF-d8): δ 8.79 (s, 1H), 8.22 (d, J=8.4 Hz, 2H), 8.15-8.18 (m, 2H), 8.00-8.06 (m, 4H), 7.88 (t, J=8.1 Hz, 1H) 7.71 (d, J=7.9 Hz, 2H), 7.41-7.49 (m, 4H), 7.25-7.34 (m, 4H).

Example 4

[0343] ##STR02003##

[0344] a) 7.78 g (25 mmol) 1-bromo-3-iodo-benzene, 16.3 g (50.0 mmol) caesium carbonate, 1.24 g (6.50 mmol) copper(I) iodide and 1.50 g (13.0 mmol) L-proline are added to 5.18 g (25.0 mmol) mmol) 5H-benzimidazo[1,2-a]benzimidazole in 100 ml dimethylsulfoxide (DMSO) under nitrogen. The reaction mixture is stirred for 18 h at 100° C. The reaction mixture is poured into water. The organic phase is extracted with dichloromethane. The organic phase is dried with magnesium sulfate. The solvent is distilled of. Column chromatography on silica gel with toluene gives the product. Yield 8.35 g (92%).

[0345] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.25 (s, 1H), 7.90-8.05 (m, 3H), 7.95-8.05 (m, 3H), 7.71 (d, J=7.9 Hz, 1H), 7.65 (d, J=7.9 Hz, 1H). 7.50-7.65 (m, 2H), 7.26-7.45 (m, 4H).

##STR02004##

[0346] b) 1.09 g (3.00 mmol) of the product of example 4a). 690 mg (2.70 mmol) 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2-dioxaborolane, 5.86 g (1.80 mmol) potassium carbonate in 20 ml DMF are degassed with argon. 1,1′-Bis(diphenylphosphino) ferrocen)dichloropalladium(II) are added and the reaction mixture is degassed with argon. The reaction mixture is stirred for 18 h at 80° C. The product is filtered off and washed with dimethylformamide (DMF), water and methanol. Yield 370 mg (44%).

[0347] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.43 (s, 2H), 7.95-8.10 (m, 6H) 7.70-7.90 (m, 6H), 7.63 (d, J=7.6 Hz, 2H), 7.20-7.45 (m, 8H).

Example 5

[0348] ##STR02005##

[0349] a) 5.78 g (16.0 mmol) of the product of example 4a). 12.16 g (47.8 mmol) 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2-dioxaborolane, 12.5 g (0.128 mol) potassium acetate in 50 ml DMF are degassed with argon. 1,1′-Bis(diphenylphosphino) ferrocen)dichloropalladium(II) are added and the reaction mixture is degassed with argon. The reaction mixture is stirred for 22 h at 60° C. and poured into a saturated solution of sodium chloride in water. The water phase is extracted with tetrahydrofuran (THF), the organic phase is dried with magnesium sulfate and the solvent is distilled off. The product is crystallized from diethyl ether and cyclohexane. Yield 3.62 g (59%).

[0350] .sup.1H NMR (400 MHz, THF-d8): δ 8.26 (s, 1H), 8.09-8.10 (m, 1H), 8.07-8.09 (m, 2H), 7.86 (s, J=7.6 Hz, 1H), 7.60-7.67 (m, 3H), 7.28-7.42 (m, 4H), 1.39 (s, 12H).

##STR02006##

[0351] b) 2.72 g (6.01 mmol) 5-(8-bromodibenzofuran-2-yl)benzimidazolo[1,2-a]benzimidazole and 6.92 g (3.01 mmol) potassium phosphate tribasic monohydrate, 27 ml dioxane, 100 ml toluene and 21 ml water are added to 3.20 g (7.82 mmol) of 5-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl] benzimidazolo[1,2-a]benzimidazole. The mixture is degassed with argon. 148 mg (0.361 mmol) 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos) and 135 mg (0.060 mmol) palladium(II) acetate are added. The reaction mixture is degassed with argon and is stirred for 22 h at 100° C. under argon. 110 ml of a 1% sodium cyanide solution are added and the reaction mixture is refluxed for 1 h. Dichloromethane is added, the organic phase is washed with water and dried with magnesium sulfate. The product is decocted with methanol (yield: 1.62 g (41%)).

[0352] .sup.1H NMR (400 MHz, THF-d8): δ 8.69 (d, J=1.1 Hz, 1H), 8.57 (d, J=1.6 Hz, 1H), 8.42 (s, 1H), 8.05-8.08 (m, 1H), 7.89-7.99 (m, 6H), 7.80-7.85 (m, 2H), 7.76-7.75 (m, 4H), 7.57-7.61 (m, 2H), 7.18-7.37 (m, 8H).

Example 6

[0353] ##STR02007##

[0354] a) 20.0 g (78.8 mmol) 1,3-dibromo-5-fluoro-benzene, 16.3 g (78.8 mmol) 6H-benzimidazolo[1,2-a]benzimidazole and 43.5 g (0.315 mmol) potassium carbonate in 200 ml DMF are stirred for 17 h at 170° C. The reaction mixture is filtered hot and the precipitate from the mother liquor is filtered after cooling. The product is washed with water and ethanol and decocted with diethyl ether and ethanol. Yield 21.2 g (61%).

[0355] .sup.1H NMR (400 MHz, THF-d8): δ 8.21-8.26 (m, 4H), 7.98-7.8.00 (m, 1H), 7.68-7.73 (m, 2H), 7.31-7.49 (m, 4H).

##STR02008##

[0356] b) 2.00 g (4.53 mmol) 5-(3,5-dibromophenyl)benzimidazolo[1,2-a]benzimidazole and 4.15 g (3.00 mmol) potassium carbonate, 27 ml dioxane, 100 ml toluene and 21 ml water are added to 3.20 g (7.82 mmol) of 2-dibenzofuran-2-yl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. The mixture is degassed with argon. 37 mg (0.090 mmol) 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos) and 10 mg (0.0045 mmol) palladium(II) acetate are added. The reaction mixture is degassed with argon and is stirred under argon for 19 h at 120° C. 110 ml of a 1% sodium cyanide solution are added and the reaction mixture is refluxed for 1 h. The solvent is distilled off. 30 ml toluene are added, the product is filtered off, washed with water and cyclohexane and crystallized from methyl butyl ketone (MEK). Yield 1.84 g (66%).

[0357] .sup.1H NMR (400 MHz, THF-d8): δ 8.21-8.26 (m, 4H), 7.98-7.8.00 (m, 1H), 7.68-7.73 (m, 2H), 7.31-7.49 (m, 4H).

Example 7

[0358] ##STR02009##

[0359] The product of Example 7 is prepared in analogy to the procedure described in example 6.

[0360] .sup.1H NMR (400 MHz, DMSO-d6): δ 8.59 (d, J=1.5 Hz, 2H), 8.46-8.47 (m, 1H), 8.24-8.33 (m, 6H), 8.13 (d, J=8.0 Hz, 1H), 7.99-8.01 (m, 2H), 7.78 (d, J=8.2 Hz, 2H), 7.37-7.68 (m, 9H), 7.29-7.37 (m, 2H)

Example 8

[0361] ##STR02010##

[0362] 3.85 g (8.51 mmol) 5-(8-bromodibenzofuran-2-yl)benzimidazolo[1,2-a]benzimidazole and 10.3 g (4.26 mmol) potassium phosphate tribasic monohydrate, 20 ml dioxane, 80 ml xylene and 16 ml water are added to 2.01 g (4.09 mmol) of 4,4,5,5-tetramethyl-2-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3,2-dioxaborolane. The mixture is degassed with argon. 210 mg (0.511 mmol) 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos) and 191 mg (0.085 mmol) palladium(II) acetate are added. The reaction mixture is degassed with argon and is stirred for 22 h at 100° C. under argon. 110 ml of a 1% sodium cyanide solution are added and the reaction mixture is refluxed for 1 h. Dichloromethane is added. The organic phase is washed with water and dried with magnesium sulfate. The product is decocted with diethylether. Yield 1.31 g (39%).

[0363] .sup.1H NMR (400 MHz, DMF-d7): δ 8.90 (d, J=1.7 Hz, 2H), 8.86 (d, J=2.2 Hz, 2H), 8.37 (s, 1H), 8.26-8.31 (m, 4H), 8.14-8.21 (m, 4H), 8.08-8.11 (m, 2H), 7.94-7.96 (m, 2H), 7.89-7.93 (m, 2H), 7.76-7.78 (m, 2H), 7.66-7.71 (m, 3H), 7.32-7.49 (m, 8H)

Example 9

[0364] ##STR02011##

[0365] a) 2,6-Diiodo-dibenzofuran is prepared according to Example 13 of WO2011/111423 and purified by crystallisation from cyclohexane.

##STR02012##

[0366] b) The product of Example 9 is prepared in analogy to the procedure described in Example 5.

Example 10

[0367] ##STR02013##

[0368] 4.20 g (10 mmol) 2,8-diiododibenzofuran, 13.0 g (40.0 mmol) caesium carbonate, 1.90 g (1.00 mmol) copper(I) iodide and 2.30 g (20.0 mmol) L-proline are added to 4.56 g (22.0 mmol) mmol) 5H-benzimidazo[1,2-a]benzimidazole in 100 ml dimethylsulfoxide (DMSO) under nitrogen. The reaction mixture is stirred for 24 h at 100° C., filtered and washed with dichloromethane. The organic phase is dried with magnesium sulfate and the solvent is distilled off. The product is crystallized form ether. Yield 4.7 g (81%)

[0369] .sup.1H NMR (400 MHz, THF-d8): δ 8.73 (d, J=1.2 Hz, 2H), 8.14 (d, J=2.3 Hz, J=8.8 Hz, 2H), 7.96-8.02 (m, 4H), 7.92 (d, J=8.8 Hz, 2H), 7.70-7.73 (m, 2H), 7.62 (d, J=7.1 Hz, 2H), 7.25-7.40 (m, 8H).

Example 11

[0370] ##STR02014##

[0371] a) 2-Bromo-dibenzofuran is prepared according E. Hand, J. Org. Chem. 62 (1997) 1348 and purified by crystallization from tert-butyl methyl ether (TBME).

##STR02015##

[0372] b) 47.27 g (0.199 mol) of 2-Bromo-benzofuran are dissolved in 440 ml dry THE and cooled to −78° C. under argon. Within 1 h a solution of lithium diisopropylamide (LDA; prepared from 81.2 ml (0.219 mol) n-butyllithium (2.7M in heptane) and 20.18 g (0.199 mol) Diisopropylamin in 250 ml of dry THF) is added, keeping the temperature below −73° C. The resulting yellow solution is stirred for 2 h at −78° C. A solution of 50.6 g (0.199 mol) iodine dissolved in 150 ml dry THE is then added within 50 minutes, keeping the temperature below −73° C. The resulting brown solution is warmed to room temperature, poured into 500 ml of buffer solution pH=7 and neutralized to pH=7 with 2N HCl. The organic solvent is evaporated and the aqueous phase extracted three times with ethylacetate. The combined organic phases are washed three times with water, dried with magnesium sulfate, filtered and the solvent is evaporated. Two crystallizations from cyclohexane/TBME=1:1 result in 35.0 g of 2-bromo-4-iodo-dibenzofuran (yield: 45.6%).

[0373] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 7.99 (d, J=1.8 Hz, 1H), 7.95 (d, J=1.8 Hz, 1H), 7.85 (d, J=8 Hz, 1H), 7.63 (d, J=8 Hz, 1H), 7.51 (t, J=8 Hz, 1H), 7.37 (t, J=8 Hz, 1H).

Example 12

[0374] ##STR02016##

[0375] a) 4-Bromo-dibenzofuran is prepared according to Example 1 of US2011/0006670 and purified by crystallisation from methanol.

##STR02017##

[0376] b) 6-Bromo-2-iodo-dibenzofuran is prepared according to Example 1 of US2011/0006670 and purified by crystallisation from 2-propanol.

##STR02018##

[0377] c) 1.00 g (2.68 mmol) 6-bromo-2-iodo-dibenzofuran, 1.75 g (5.36 mmol) caesium carbonate, 130 mg (0.67 mmol) copper(I) iodide and 150 mg (1.34 mmol) L-proline are added to 670 mg (3.22 mmol) 5H-benzimidazo[1,2-a]benzimidazole in 20 ml DMSO under nitrogen. The reaction mixture is stirred for 18 h at 100° C. and filtered. THF and toluene are added to the organic phase and the organic phase is washed with water. The organic phase is dried with magnesium sulfate and the solvent is distilled off. The product can be used without further purification in step d) (yield=650 mg (78%)).

[0378] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.66 (d, J=2.2 Hz, 1H), 8.13-8.19 (m, 2H), 7.96-8.07 (m, 3H), 7.66-7.78 (m, 3H), 7.25-7.45 (m, 5H).

##STR02019##

[0379] d) The product of Example 12 is prepared in analogy to the procedure described in Example 5. MS (APCl(pos), m/z): 615.5 (M.sup.+1). .sup.1H NMR (400 MHz, THF-d8): 8.68 (d, J=2.1 Hz, 1H), 8.34 (t, J=1.8 Hz, 1H), 8.21 (d, J=7.7 Hz, 3H), 7.85-7.15 (m, 7H), 7.65-7.77 (m, 5H), 7.47-7.58 (m, 3H), 7.28-7.44 (m, 6H).

Example 13

[0380] ##STR02020##

[0381] The synthesis of 9-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbazole is described in Chem. Mater. 20 (2008) 1691-1693. The product of Example 21 is prepared in analogy to the procedure described in Example 5.

Example 14

[0382] ##STR02021##

[0383] 2-Iodo-dibenzofuran is prepared according to A. Kryska, Journal of Chemical Research, Miniprint 10 (1999) 2501 and purified by crystallisation from methanol.

Example 15

[0384] ##STR02022##

[0385] a) 2,4-Diiodo-dibenzofuran is prepared in analogy to the procedure described in Example 11, starting from 2-iodo-dibenzofuran (Example 14) and purified by crystallisation from 2-propanol (yield: 80%).

[0386] .sup.1H NMR (400 MHz, CDCl.sub.3): δ 8.17 (s, 1H), 8.07 (s, 1H), 7.84 (d, J=7.6 Hz, 1H), 7.63 (d, J=7.6 Hz, 1H), 7.51 (t, J=7.6 Hz, 1H), 7.37 (t, J=7.6 Hz, 1H).

##STR02023##

[0387] b) The product of Example 15 is prepared in analogy to the procedure described in Example 10.

Example 16

[0388] ##STR02024##

[0389] a) 7.00 g (24.7 mmol) 1-bromo-4-iodo-benzene, 10.5 g (32.2 mmol) caesium carbonate, 2.36 g (12.4 mmol) copper(I) iodide and 2.85 g (24.7 mmol) L-proline are added to 5.13 g (24.7 mmol) mmol) 5H-benzimidazo[1,2-a]benzimidazole in 80 ml DMSO under nitrogen. The reaction mixture is stirred for 15 h at 100° C. and 4 h at 150° C., filtered on Hyflo with dichloromethane. The organic phase is washed with water. The organic phase is dried with magnesium sulfate. The product is decocted with diethylether and methyl ethyl ketone (MEK). Yield: 2.90 g (77%).

[0390] .sup.1H NMR (400 MHz, DMF-d7): δ 7.93-8.10 (m, 4H), 7.78-7.92 (m, 2H), 7.72-7.79 (m, 1H), 7.49-7.71 (m, 1H), 7.31-7.49 (m, 4H).

##STR02025##

[0391] b) The product of Example 16b) is prepared in analogy to the procedure described in Example 4b).

[0392] .sup.1H NMR (400 MHz, DMF-d7): δ=8.19-8.33 (m, 10H), 7.83-7.87 (m, 2H), 7.73-7.77 (m, 2H), 7.35-7.54 (m, 4H). One signal is covered by DMF

[0393] MS (APCl(pos), m/z): 565 (M.sup.+1).

Example 17

[0394] ##STR02026##

[0395] The product of Example 17 is prepared in analogy to the procedure described in Example 4b).

Example 18

[0396] ##STR02027##

[0397] The product of Example 18 is prepared in analogy to the procedure described in Example 5b). MS (APCl(pos), m/z): 615 (M.sup.+1).

Example 19

[0398] ##STR02028##

[0399] 2 g (4.04 mmol) 3,6-diiodo-9-phenyl-carbazole, 5.26 g (16.2 mmol) caesium carbonate, 190 mg (0.101 mmol) copper(I) iodide and 233 mg (2.02 mmol) L-proline are added to 1.84 g (8.89 mmol) 5H-benzimidazo[1,2-a]benzimidazole in 40 ml DMSO under nitrogen. The reaction mixture is stirred for 10 h at 150° C., filtered on Hyflo Super Cel® medium (Fluka 56678, CAS [91053-39-3]) and washed with dichloromethane. The organic phase is dried with magnesium sulfate and the solvent is distilled off. Gradient column chromatography with cyclohexane/toluene (cyclohexane 100%, cyclohexane/toluene 10/1, cyclo-hexane/toluene 4/1) result in the product (yield: 70 mg (3%)). MS (APCl(pos), m/z): 654 (M.sup.+1).

[0400] .sup.1H NMR (400 MHz, THF-d8): δ=8.81 (d, J=1.9 Hz, 2H), 7.99-7.05 (m, 6H), 7.70-7.83 (m, 11H), 7.22-7.41 (m, 8H).

[0401] In addition to Cpd. A-12 the following compounds have been detected by HPLC-MS:

##STR02029##

(MS (APCl(pos), m/z): 449 (M.sup.+1)).

##STR02030##

(MS (APCl(pos), m/z): 575 (M.sup.+1)).

##STR02031##

[0402] a) The product of Example 20a) is prepared in analogy to the procedure described in Example 1c). Reference is made to J. Heterocyclic Compounds (1989) 168 and J. Org. Chem 42 (1977) 542 with respect to the synthesis of 4H-[1,2,4]triazolo[1,5-a]benzimidazole and the starting materials used for its synthesis. MS (MALDI-MS (, m/z: 403 (M.sup.+1).

##STR02032##

[0403] b) The product of Example 20b) is prepared in analogy to the procedure described in Example 13).

Example 21

[0404] ##STR02033##

[0405] a) 5 g (31.6 mmol) 4H-[1,2,4]triazolo[1,5-a]benzimidazole, 20.6 g (63.2 mmol) caesium carbonate, 1.5 g (7.9 mmol) copper(I) iodide, and 910 mg (7.9 mmol) L-proline are added to 17.8 g (8 mL) (63.2 mmol) 1-bromo-3-iodobenzene in 60 mL DMSO under nitrogen. The reaction mixture is stirred for 15 h at 85° C. The reaction mixture is filtered through silica gel with dichloromethane. The organic phase is washed with water, NaCl solution, and dried with sodium sulfate. The product is decocted with diethylether (yield: 8.0 g (80%)). .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): δ 8.02 (s, 1H), 7.98 (s, 1H), 7.90-7.88 (m, 1H), 7.71-7.68 (m, 1H), 7.60-7.58 (d, 1H), 7.52-7.48 (t, 1H), 7.46-7.40 (m, 2H). 13C NMR (500 MHz, CD.sub.2Cl.sub.2): δ 155.05 (d, 1C), 153.47 (s, 1C), 136.82 (s, 1C), 134.23 (s, 1C), 131.63 (d, 1C), 130.78 (d, 1C), 126.69 (d, 1C), 124.95 (s, 1C), 124.87 (d, 1C), 123.50 (s, 1C), 123.26 (d, 1C), 122.45 (d, 1C), 112.15 (d, 1C), 111.66 (d, 1C).

##STR02034##

[0406] b) 1.25 g (4 mmol) 4-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]benzimidazole, 2.4 g (5.2 mmol) 9-[8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzofuran-2-yl]carbazole, and 4.3 g (20 mmol) potassium phosphate in 40 mL toluene are added to 90 mg (0.03 mmol) palladium(II) acetate, 100 mg (0.24 mmol) 2-dicyclohexylphosphino-2,6-dimethoxybiphenyl (SPhos) in dioxane/water 40 mL/10 mL under argon. The reaction mixture is stirred for 15 h at 85° C. and filtered through celite with dichloromethane. The organic phase is washed with water, NaCl solution, and dried with sodium sulfate (yield: 1.75 g (77%)).

[0407] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): δ 8.41 (d, 1H), 8.37 (d, 1H), 8.34 (d, 2H), 8.25 (t, 1H), 8.17 (s, 1H), 8.06-8.04 (m, 3H), 7.93-7.86 (m, 4H), 7.84 (d, 1H), 7.82 (d, 1H), 7.59-7.54 (m, 6H), 7.47-7.43 (m, 2H). .sup.13C NMR (500 MHz, CD.sub.2Cl.sub.2): δ 157.22 (s, 1C), 155.97 (s, 1C), 155.07 (d, 1C), 153.80 (s, 1C), 143.30 (s, 1C), 141.80 (s, 2C), 136.12 (s, 1C), 135.79 (s, 1C), 134.68 (s, 1C), 133.14 (s, 1C), 130.81 (d, 1C), 127.78 (d, 1C), 127.31 (d, 1C), 126.79 (d, 1C), 126.36 (d, 2C), 125.87 (s, 1C), 124.91 (s, 1C), 124.89 (s, 1C), 124.76 (d, 1C), 123.51 (d, 2C), 122.92 (d, 1C), 122.88 (d, 1C), 120.61 (d, 2C), 120.31 (d, 1C), 120.26 (d, 2C), 122.65 (d, 1C), 120.03 (d, 1C), 113.40 (d, 1C), 112.66 (d, 1C), 112.21 (d, 1C), 111.58 (d, 1C), 110.02 (d, 2C).

Example 22

[0408] ##STR02035##

[0409] 160 mg (0.48 mmol) 1,3-diiodobenzene and 170 mg (1.06 mmol) 4H-[1,2,4]triazolo[1,5-a]benzimidazole in 10 mL DMSO are stirred under argon for 15 minutes. 625 mg (1.9 mmol) caesium carbonate, 120 mg (1.06 mmol) L-proline, and 90 mg (0.48 mmol) copper(I) iodide are added. The reaction mixture is stirred for 15 h at 100° C. and filtered through celite with dichloromethane. The organic phase is washed with water, NaCl solution, and dried with sodium sulfate. The product is crystallized from isopropanol (yield: 130 mg (69%)). .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): δ 8.35 (s, 1H), 8.06 (s, 2H), 7.94-7.84 (m, 7H), 7.50-7.42 (m, 4H). .sup.13C NMR (500 MHz, CD.sub.2Cl.sub.2): δ 155.12 (d, 2C), 153.59 (s, 2C), 137.10 (s, 2C), 134.27 (s, 2C), 131.07 (d, 1C), 125.09 (s, 2C), 125.06, (d, 2C), 123.39 (d, 2C), 121.80 (d, 2C), 118.36 (d, 1C), 112.51 (d, 2C), 111.73 (d, 2C).

Example 23

[0410] ##STR02036##

[0411] 1 g (2.4 mmol) 2,8-diiodedibenzofuran and 840 mg (5.3 mmol) 4H-[1,2,4]triazolo[1,5-a]benzimidazole in 10 mL DMSO are stirred under argon for 15 minutes. 3.1 g mg (9.6 mmol) caesium carbonate, 550 mg (4.8 mmol) L-proline, and 460 mg (2.4 mmol) copper(I) iodide are added. The brown reaction mixture is stirred for 15 h at 100° C. Water is added to the reaction mixture and filtered and washed with methanol. The product is crystallized from toluene (yield: 330 mg (28%)). .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): δ 8.38 (s, 1H), 8.05 (s, 2H), 7.92-7.85 (m, 8H), 7.42-7.13 (dd, 2H)

Example 24

[0412] 9-(9H-Carbazol-3-yl)-9H-carbazole is prepared according to a literature procedure (J. Org. Chem, 2008, 73, 1809).

##STR02037##

[0413] a) The product of Example 24a) is prepared according to the procedure of Example 10. Purification: FC (SiO.sub.2, cyclohexane/CH.sub.2Cl.sub.2 4:1. Yield: 85%.

[0414] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): δ 8.34 (s, 1H), 8.18 (m, 5H), 7.87 (d, 1H), 7.77 (d, 1H), 7.67 (d, 1H), 7.59 (m, 3H), 7.51-7.39 (m, 6H), 7.31 (m, 3H).

##STR02038##

[0415] b) Pd(dppf)*CH.sub.2Cl.sub.2 (8 mg, 0.01 mmol) is added to a degassed (Ar) mixture of 5-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl] benzimidazolo[1,2-a]benzimidazole (133 mg, 0.33 mmol), the product of Example 24a) (144 mg, 0.25 mmol) in dioxane (5 mL) and NaOH (3 M, 0.25 mL). The reaction mixture is heated for 8 h at 80° C. and filtered over Celite and FC (SiO.sub.2, CH.sub.2Cl.sub.2) gives the product (yield: 50 mg, 26%).

[0416] .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2): δ 8.33 (2×s, 2+1H), 8.18 (m, 4H), 7.88 (m, 5H), 7.81-7.73 (m, 4H), 7.69-7.62 (m, 3H), 7.56 (d, 1H), 7.49 (d, 2H), 7.42-7.27 (m, 11H).

Application Example 3

[0417] The preparation of the ITO substrate as well as the later characterization of the complete diode is equivalent to Application Example 1, except that the composition of the following layers differs:

[0418] As a hole transport and exciton blocker, Ir(dpbic).sub.3, is applied to the substrate with a thickness of 20 nm, wherein the first 10 nm are doped with MoO.sub.3 (˜10%) to improve the conductivity. Subsequently, a mixture of 30% by weight of emitter compound,

##STR02039##

15% by weight of compound Ir(dpbic).sub.3 and 55% by weight of compound

##STR02040##

is applied by vapor deposition in a thickness of 30 nm.

[0419] Subsequently, compound A-10 is applied by vapour deposition with a thickness of 5 nm as hole blocker. Subsequently a mixture of 50% by weight of material

##STR02041##

and 50% by weight of material

##STR02042##

is evaporated as electron transporting layer with a thickness of 20 nm. Finally ˜2 nm KF are deposited as electron injection layer and a 100 nm thick Al electrode completes the device.

Comparative Application Example 1

[0420] The production and construction of the OLED is done as in Application Example 3, except for the following: The doping concentration of MoO.sub.3 in Ir(dpbic).sub.3 in the hole transport layer is 5% by weight. The emissive layer consists of 30% by weight of compound

##STR02043##

15% by weight of compound Ir(dpbic).sub.3 and 55% by weight of compound

##STR02044##

The hole blocking layer consists of compound Ref-1 and the electron transporting layer is 25 nm thick.

TABLE-US-00013 Voltage EQE Host @ 300 nits @ 300 nits Lifetime material [V] [%] @ 4000 nits* Appl. Ex. 3 A-10 4.02 14.0% 100 Comp. Appl. Ex. 1 Ref-1 4.00 10.8%  20 *The measured lifetime of Application Example 3 is set to 100 and the lifetime of Comparative Application Example 1 is specified in relation to those of Application Example 3.

Application Example 4

[0421] The production and construction of the OLED is done as in Application Example 3, except for the following: The hole transporting layer with MoO.sub.3 and Ir(dpbic).sub.3 is 15 nm and the undoped electron blocker, Ir(dpbic).sub.3, is only 5 nm thick. The emissive layer consists of 30% by weight of compound

##STR02045##

10% by weight of compound Ir(dpbic).sub.3 and 60% by weight of compound

##STR02046##

the thickness is 40 nm.

[0422] The hole blocking layer consists of material B-5.

Comparative Application Example 2

[0423] The production and construction of the OLED is done as in Application Example 3, except for the following: The emissive layer consists of 30% by weight of compound

##STR02047##

10% by weight of compound Ir(dpbic).sub.3 and 60% by weight of compound

##STR02048##

the thickness is 40 nm. The hole blocking layer consists of compound Ref-2.

TABLE-US-00014 Voltage Host @ 300 nits Lifetime material [V] @ 4000 nits* Appl. Ex. 4 B-5 4.55 100 Comp. Appl. Ex. 2 Ref-2 4.34  70 *The measured lifetime of Application Example 4 is set to 100 and the lifetime of Comparative Application Example 2 is specified in relation to those of Application Example 4.

Application Example 5

[0424] The production and construction of the OLED is done as in Application Example 1, except for the following: The emissive layer consists of 30% by weight of compound

##STR02049##

10% by weight of compound Ir(dpbic).sub.3 and 60% by weight of compound

##STR02050##

the thickness is 30 nm. The electron transporting layer is 25 nm thick.

Comparative Application Example 3

[0425] The production and construction of the OLED is done as in Application Example 1, except for the following: The emissive layer consists of 30% by weight of compound

##STR02051##

[0426] 10% by weight of compound Ir(dpbic).sub.3 and 60% by weight of compound

##STR02052##

the thickness is 30 nm. The electron transporting layer is 25 nm thick.

TABLE-US-00015 Voltage EQE Host @ 300 nits @ 300 nits material [V] [%] Appl. Ex. 5 A-20 3.43 11.3 Comp. Appl. Ex. 3 Ref-3 3.81 13.6 *The measured lifetime of Application Example 5 is set to 100 and the lifetime of Comparative Application Example 3 is specified in relation to those of Application Example 5.

Application Example 6

[0427] The production and construction of the OLED is done as in Application Example 3, except for the following: The emissive layer consists of 30% by weight of compound

##STR02053##

10% by weight of compound Ir(dpbic).sub.3 and 60% by weight of compound

##STR02054##

the thickness is 40 nm. The hole blocking layer consists of material A-3.

TABLE-US-00016 Voltage EQE Host @ 300 nits @ 300 nits material [V] [%] CIE Appl. Ex. 6 A-20 4.56 12.8 0.18/0.36