New Heterocyclic bridged biphenyls

1 . An electroluminescent (EL) device, comprising a compound of the formula

wherein A is a 5-, 6-, or 7-membered heteroaromatic ring, containing at least one heteroatom selected from nitrogen, oxygen and sulfur,

Z 1 is

 NA 1 A 1′ , —P(═O)A 4 A 4′ , or —SiA 6 A 7 A 8 ,

Z 2 is

 —NA 2 A 2′ , —P(═O)A 5 A 5′ , or —SiA 6′ A 7′ A 8′ ,

Ar and Ar′ are independently of each other C 6 -C 14 aryl which may optionally be substituted by one or more groups selected from C 1 -C 25 alkyl which may optionally be interrupted by —O—, or C 1 -C 25 alkoxy,

R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently of each other hydrogen, halogen, or an organic substituent, or

R 1 and R 2 , R 4 and R 6 , R 2 and R 3 , R 5 and R 3 and/or R 5 and R 6 , which are adjacent to each other, together form an aromatic or heteroaromatic ring or ring system which can optionally be substituted,

R 7 is an organic substituent, wherein two or more substituents R 7 in the same molecule may have different meanings, or can form together an aromatic or heteroaromatic ring or ring system, and

x is 0, or an integer of 1 to 5;

A 1 , A 2 , A 1′ and A 2′ are independently of each other a C 6 -C 24 aryl group, a C 2 -C 30 heteroaryl group, which can optionally be substituted, or a group

 wherein BU is a bridging unit, A 3 and A 3′ are independently of each other a C 6 -C 24 aryl group or a C 2 -C 30 heteroaryl group, which can optionally be substituted, or A 1 and A 1′ or A 2 and A 2′ or A 3 and A 3′ together with the nitrogen atom to which they are bonded form a heteroaromatic ring or ring system

A 4 , A 4′ , A 6 , A 7 , A 8 , A 5 , A 5′ , A 6′ , A 7′ , and A 8′ are independently of each other a C 6 -C 24 aryl group or a C 2 -C 30 heteroaryl group, which can optionally be substituted.

2 . The EL device according to claim 1 , comprising a compound of formula

R 1 and R 4 are independently of each other hydrogen, halogen, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, 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 and/or interrupted by D, CN, or —CO—R 28 ,

R 2 , R 3 , R 5 and R 6 are independently of each other H, halogen, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, 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 and/or interrupted by D, C 7 -C 25 aralkyl, CN, or —CO—R 28 ,

R 8 and R 9 are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, 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 and/or interrupted by D, C 7 -C 25 aralkyl, CN, or —CO—R 28 , or

R 8 and R 9 together form a group

 wherein R 206′ , R 208′ R 205 , R 206 , R 207 , R 208 , R 209 and R 21 are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, C 1 -C 18 alkoxy, or C 1 -C 18 alkoxy which is substituted by E and/or interrupted by D, 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 7 -C 25 aralkyl, CN, or —CO—R 28 ,

R 10 is H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, 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 and/or interrupted by D, C 7 -C 25 aralkyl, or —CO—R 28 ,

R 8′ and R 9′ are independently of each other H, CN, —COOR 27 ; —CONR 25 R 26 , C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, 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 and/or interrupted by D, C 7 -C 25 aralkyl, CN, or —CO—R 28 ;

R 11 and R 14 are independently of each other hydrogen, halogen, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, 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 and/or interrupted by D, CN, or —CO—R 28 ,

R 12 , R 13 , R 15 and R 16 are independently of each other H, halogen, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, 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 and/or interrupted by D,

C 7 -C 25 aralkyl, CN or —CO—R 28 ,

X is O, S, or NR 17 , wherein R 17 is H; C 6 -C 18 aryl; C 2 -C 20 heteroaryl; C 6 -C 18 aryl or C 2 -C 20 heteroaryl which are substituted by C 1 -C 18 alkyl, C 1 -C 18 perfluoroalkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—;

or two substituents R 1 and R 2 , R 4 and R 6 , R and R 12 and/or R 14 and R 6 , R 2 and R 3 , R 5 and R 6 , R 12 and R 13 , and/or R 15 and R 16 , which are adjacent to each other, together form a group

 or two substituents R 15 and R 13 , and/or R 5 and R 3 , which are adjacent to each other, together form a group

 wherein X 3 is O, S, C(R 119 )(R 120 ), or NR 17 , 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 and/or interrupted by D, C 1 -C 18 alkoxy, or C 1 -C 18 alkoxy which is substituted by E and/or interrupted by D,

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 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, 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 and/or interrupted by D, 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 and/or interrupted by D, 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, which optionally can be substituted by 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 14 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 and/or interrupted by D, C 7 -C 25 aralkyl, or —C(═O)—R 2 , and

R 127 is H; 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—; and

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 and/or interrupted by D,

wherein R 23 , R 24 , R 25 and R 26 are independently of each other H; 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 H; 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 H; 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.

3 . The EL device according to claim 2 , comprising a compound of the formula X, or XI, wherein R and R 4 are hydrogen,

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 interrupted by D, C 1 -C 18 perfluoroalkyl, C 1 -C 18 alkoxy, C 1 -C 18 alkoxy which is interrupted by D, C 7 -C 25 aralkyl, or a group —X 2 —R 18 ,

R 8 and R 9 are independently of each other H, 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, C 1 -C 18 alkoxy which is interrupted by D, or a group —X 2 —R 18 ; or two substituents R and R 3 and/or R 5 and R 6 , which are adjacent to each other, together form a group

 or two substituents R 5 and R 3 , which are adjacent to each other, together form a group

 wherein R 105 , R 106 , R 107 and —R 108 are independently of each other H, or C 1 -C 8 alkyl, or

R 8 and R 9 together form a group

 wherein R 205 , R 206 , R 207 , R 208 , R 209 and R 210 are independently of each other H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, C 1 -C 18 alkoxy, or C 1 -C 18 alkoxy which is substituted by E and/or interrupted by D, C 1 -C 18 perfluoroalkyl,

R 10 is H, C 6 -C 18 aryl, which can be substituted by G, C 2 -C 18 heteroaryl, which can be substituted by G, 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, C 1 -C 18 alkoxy which is substituted by E and/or interrupted by D, or a group —X 2 —R 18 ,

wherein X 2 is a C 6 -C 12 aryl, or C 6 -C 12 heteroaryl spacer, which can be substituted one to two times with 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 and/or interrupted by D,

and R 18 is H, 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, C 1 -C 18 alkoxy which is interrupted by D, or —NR 25 R 26 ;

D is —CO—; —COO—; —S—; —SO—; —SO 2 —; —O—; —NR 25 —; —CR 23 ═CR 24 —; or —C≡C—; wherein

R 23 , R 24 , R 25 and R 26 are independently of each other H; C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 8 alkyl or C 1 -C 8 alkoxy; C 1 -C 8 alkyl; or C 1 -C 8 alkyl which is interrupted by —O—, or R 25 and R 26 together form a five or six membered ring.

4 . The EL device according to claim 2 , comprising a compound having the formula

wherein R 10 is H, C 6 -C 18 aryl which can be substituted by G, C 2 -C 18 heteroaryl which can be substituted by G, 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, C 1 -C 18 alkoxy which is substituted by E and/or interrupted by D, or a group —X 2 —R 18 , wherein X 2 is a C 6 -C 12 aryl or C 6 -C 12 heteroaryl spacer which can be substituted one to two times with 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 and/or interrupted by D, and R 18 is H, 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, C 1 -C 18 alkoxy which is interrupted by D, or —NR 25 R 26 —;

R 11 and R 14 are hydrogen,

R 12 , R 13 , R 15 and R 16 are hydrogen,

R 17 is C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, C 1 -C 18 perfluoroalkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—; or

two substituents R 15 and R 13 , R 12 and R 13 and/or R 15 and R 16 , which are adjacent to each other, together form a group

 or two substituents R 15 and R 13 , which are adjacent to each other, together form a group

 wherein R 105 , R 10 , R 107 and R 108 are independently of each other H, or C 1 -C 8 alkyl,

D is —S—; —O—; or —NR 25 —;

E is —OR 29 ; —SR 29 ; —NR 25 R 26 ; —CN; or F;

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 and/or interrupted by D, wherein

R 25 and R 26 are independently of each other H; C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 8 alkyl or C 1 -C 8 alkoxy; C 1 -C 8 alkyl; or C 1 -C 8 alkyl which is interrupted by —O—, or

R 25 and R 26 together form

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—.

5 . The EL device according to claim 1 , wherein A 1 , A 2 , A 1′ and A 2′ are independently of each other

 or A 1 and A 1′ or 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 occurence and is 0, 1, 2, or 3;

R 41 can be the same or different at each occurence 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 in neighbourhood to each other could be 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 in neighbourhood 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,

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 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, 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 and/or interrupted by D, C 7 -C 25 aralkyl, —C(═O)—R 127 , —C(═O)OR 127 , or —C(═O)NR 127 R 128 , 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 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, 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 and/or interrupted by D, 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 and/or interrupted by D, 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, which optionally can be substituted by 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, 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 and/or interrupted by D, C 7 -C 25 aralkyl, or —C(═O)—R 127 , and

R 126 and R 127 are independently of each other H; 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 65 , —SiR 70 R 71 —, POR 72 —, —CR 63 ═CR 64 —, or —C≡C—, and

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 C 1 -C 18 alkyl,

R 63 , R 64 , R 65 , R 65 and R 66 are independently of each other H; 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 65 and R 66 together form a five or six membered ring,

R 67 and R 68 are independently of each other H; 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 69 is H; 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 70 and R 71 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 72 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; or

A 1 , A 2 , A 1′ and A 2′ are independently of each other a group

 wherein BU is

or

6 . The EL device according to claim 1 , comprising a compound selected from

7 . Electroluminescent device according to claim 1 , comprising a cathode, an anode, and therebetween a light emitting layer containing a host material and a phosphorescent light-emitting material, wherein the host material is a compound of formula I.

8 . A compound of the formula

wherein

A, Z 1 , Z 2 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and x are as defined in claim 1 , with the proviso that phenazine compounds expressed by formula

are excluded, wherein each R 1 -R 4 is an H atom, a (substituted)alkyl group, aralkyl group, aryl group, or heterocyclic group, wherein R 1 and R 2 , and R 3 and R 4 may form a 5-7 membered ring together with an N atom, respectively; each R 5 -R 7 is an H atom, (substituted)alkyl group, alkoxy group, halogen atom or nitro group.

9 . Solar cells, dye lasers or electroluminescent devices comprising a compound of formula I according to claim 8 .

10 . A process for the preparation of compounds of the formula Ia or Ib according to claim 12 , wherein Z 1 and Z 2 are independently of each other —NA 1 A 1′ , or

m′ is 0, 1, or 2; which comprises reacting a compound of formula

wherein X 10 stands for halogen, with a compound of formula HNA 1 A 1′ , or

in the presence of a base and a catalyst in a solvent.

11 . An electroluminescent (EL) device according to claim 1 , comprising a compound of the formula

wherein A is a 5-, 6-, or 7-membered heteroaromatic ring, containing one nitrogen atom and at least one further heteroatom selected from nitrogen, substituted nitrogen, oxygen and sulfur,

Ar and Ar′ are independently of each other phenyl or naphthyl, which may optionally be substituted by one or more groups selected from C 1 -C 25 alkyl which may optionally be interrupted by —O— or C 1 -C 25 alkoxy,

A 1 , A 2 , A 1′ and A 2′ are independently of each other a C 6 -C 24 aryl group, a C 2 -C 30 heteroaryl group, which can optionally be substituted, or a group

 wherein BU is

A 3 and A 3′ are independently of each other a C 6 -C 24 aryl group or a C 2 -C 30 heteroaryl group, which can optionally be substituted,

or A 1 and A 1′ or A 2 and A 2′ or A 3 and A 3′ together with the nitrogen atom to which they are bonded form a heteroaromatic ring system

 m′ is 0, 1, or 2;

R 41 can be the same or different at each occurence and is Cl, F, CN, NR 45 R 45′ , 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 in neighbourhood 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 21 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 and R 45′ are independently of each other 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 in neighbourhood 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,

m can be the same or different at each occurence and is 0, 1, 2, or 3.

12 . A compound according to claim 8 , of the formula

wherein A is a 5-, 6-, or 7-membered heteroaromatic ring, containing one nitrogen atom and at least one further heteroatom selected from nitrogen, substituted nitrogen, oxygen and sulfur,

Ar and Ar′ are independently of each other phenyl or naphthyl, which may optionally be substituted by one or more groups selected from C 1 -C 25 alkyl which may optionally be interrupted by —O— or C 1 -C 25 alkoxy,

A 1 , A 2 , A 1′ and A 2′ are independently of each other a C 6 -C 24 aryl group, a C 2 -C 30 heteroaryl group, which can optionally be substituted, or a group

 wherein BU is

A 3 and A 3′ are independently of each other a C 6 -C 24 aryl group or a C 2 -C 30 heteroaryl group, which can optionally be substituted,

or A′ and A 1′ or A 2 and A 2′ or A 3 and A 3′ together with the nitrogen atom to which they are bonded form a heteroaromatic ring system

 m′ is 0, 1, or 2;

R 41 can be the same or different at each occurence and is Cl, F, CN, NR 45 R 45′ , 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 in neighbourhood 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 , or two or more groups R 41 form a ring system;

R 45 and R 45′ are independently of each other 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 in neighbourhood 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,

m can be the same or different at each occurence and is 0, 1, 2, or 3.