Heterocyclic bridged biphenyls
The present invention relates to compounds of the formula (I), a process for their preparation and their use in organic light emitting diodes (OLEDs), especially as host for phosphorescent compounds. The hosts may function with phosphorescent materials to provide improved efficiency, stability, manufacturability, or special characteristics of electroluminescent devices.
1. A compound of the formula
wherein A is
R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently of each other hydrogen, F, 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,
x is 0, or an integer of 1 to 5;
R 7 has the meaning of R 8 ,
R 8″ has the meaning of R 8 ,
p is 0, 1, 2, or 3,
the dotted line - - - indicates the bonding to the biphenyl unit,
R 8 and R 9 are independently of each other H, CN, 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 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, 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, F, 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 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, —N(C 6 -C 18 aryl) 2 , 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 11 and R 12 , and/or R 14 and R 16 , 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 , wherein R 17 is as defined above, 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 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 ,
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 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 is C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—,
R 28 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 29 is C 6 -C 18 aryl; C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—,
R 30 and R 31 are independently of each other C 1 -C 18 alkyl, C 6 -C 18 aryl, or C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl,
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,
Z 1 and Z 2 are independently of each other a group
wherein R 5″ is hydrogen, or has the meaning of R 6 ,
R 6″ , R 7″ , and R 9″ are independently of each other C 6 -C 18 aryl; which may optionally be substituted by G; or C 2 -C 20 heteroaryl, which may optionally be substituted by G,
X 3 represents O, S or N—R 121′ ,
X 9 represents O, S or N—R 121′ ,
Q 1 and Q 2 represents atoms necessary for forming a carbocyclic aromatic, or heterocyclic aromatic ring, which can optionally be condensed with other ring(s) to form a condensed ring, and/or can optionally be substituted by G,
R 121′ is C 6 -C 18 aryl; or C 2 -C 20 heteroaryl; which can optionally be 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—;
R 116 , 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 126 , or substituents R 116 , R 116′ , R 117 and R 117′ , which are adjacent to each other, can form a ring,
R 126 and R 127 are independently of each other C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—,
R 120 , R 123 , R 124 and R 125 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, which can optionally be substituted by G, C 2 -C 20 heteroaryl, which can optionally be 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,
R 128 is H, CN, 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, which can optionally be substituted by G, C 2 -C 20 heteroaryl, which can optionally be 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,
L 1 is a single bond, —(CR 47 ═CR 48 ) m2 —, —(Ar 3 ) m3 —, —[Ar 3 (Y 1 ) m1 ] m4 —, —[(Y 1 ) m1 Ar 3 ] m4 —, or —[Ar 3 (Y 2 ) m1 Ar 4 ] m4 —, wherein
Y 1 is —(CR 47 ═CR 48 )—,
Y 2 is NR 49 , O, S, C═O, C(═O)O, wherein R 49 is H; C 6 -C 18 aryl which can optionally be 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 47 and R 48 are independently of each other hydrogen, fluorine, C 1 -C 20 alkyl, or C 6 -C 24 aryl, which can optionally be substituted by G,
m1 is an integer of 1 to 10, m2 is an integer of 1 to 10, m3 is an integer of 1 to 5, m4 is an integer of 1 to 5,
Ar 3 and Ar 4 are independently of each other arylen, or heteroarylen, which can optionally be substituted,
X 4 , X 5 and X 6 are independently of each other N, or CH, with the proviso that at least one of the substituents X 4 , X 5 and X 6 are N,
Ar 1 and Ar 2 are independently of each other C 6 -C 24 aryl, which can optionally be substituted by G, or C 2 -C 20 heteroaryl, which can optionally be substituted by G, wherein D, E and G are as defined above, and
wherein at least one of Z 1 and Z 2 is an electron deficient heteroaryl group.
2. A compound according to claim 1 of formula
wherein
IV and R 4 are independently of each other hydrogen, F, 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, F, 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, CN, 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 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, 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, F, 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 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, —N(C 6 -C 18 aryl) 2 , 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 11 and R 12 , and/or R 14 and R 16 , 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 , wherein R 17 is as defined above, 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 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 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 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 is C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy;
C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—,
R 28 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 29 is C 6 -C 18 aryl; C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—,
R 30 and R 31 are independently of each other C 1 -C 18 alkyl, C 6 -C 18 aryl, or C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl, and
R 32 is C 1 -C 18 alkyl, C 6 -C 18 aryl, or C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl, and
Z 1 and Z 2 are as defined in claim 1 .
3. A compound of the formula X, XI, XII, XVI, XVII or XVIII, according to claim 2 , wherein R 1 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, CN, 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 2 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 as C 6 -C 12 aryl or C 6 -C 12 heteroaryl spacer, which can be substituted one or more 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. A compound according to claim 2 having the formula
wherein R 19 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′ 8 , wherein X 2 is a C 6 -C 12 aryl or C 6 -C 12 heteroaryl spacer which can be substituted one or more 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, —N(C 6 -C 18 aryl) 2 , 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 5 and R 3 , 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 106 , 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 a five or six membered ring, and
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. A compound according to claim 2 , wherein
Z 1 and Z 2 are independently of each other a group
wherein R 116 , 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 126 , or substituents R 116 , R 117 and R 117′ , which are adjacent to each other, can form a ring,
R 126 and R 127 are independently of each other C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—, and
wherein at least one of Z 1 and Z 2 is an electron deficient heteroaryl group.
6. A compound of formula:
Compound
Z 1 = Z 2
A1
HE-1
A2
HE-2
A3
HE-2
A4
HE-4
A5
HE-5
A6
HE-6
A7
HE-7
A8
HE-8
A9
HE-9
A12
AR-1
A13
AR-2
A14
AR-3
A15
AR-4
A16
SR-1
B1
HE-1
B2
HE-2
B3
HE-2
B4
HE-4
B5
HE-5
B6
HE-6
B7
HE-7
B8
HE-8
B11
HE-11
B12
AR-1
B13
AR-2
B14
AR-3
B15
AR-4
B16
SR-1
C1
HE-1
C2
HE-2
C3
HE-2
C4
HE-4
C5
HE-5
C6
HE-6
C7
HE-7
C8
HE-8
C9
HE-9
C12
AR-1
C13
AR-2
C14
AR-3
C15
AR-4
C16
SR-1
D1
HE-1
D2
HE-2
D3
HE-2
D4
HE-4
D5
HE-5
D6
HE-6
D7
HE-7
D8
HE-8
D9
HE-9
D12
AR-1
D13
AR-2
D14
AR-3
D15
AR-4
D16
SR-1
E1
HE-1
E2
HE-2
E3
HE-2
E4
HE-4
E5
HE-5
E6
HE-6
E7
HE-7
E8
HE-8
E9
HE-9
E12
AR-1
E13
AR-2
E14
AR-3
E15
AR-4
E16
SR-1
F1
HE-1
F2
HE-2
F3
HE-2
F4
HE-4
F5
HE-5
F6
HE-6
F7
HE-7
F8
HE-8
F9
HE-9
F12
AR-1
F13
AR-2
F14
AR-3
F15
AR-4
F16
SR-1
G1
HE-1
G2
HE-2
G3
HE-2
G4
HE-4
G5
HE-5
G6
HE-6
G7
HE-7
G8
HE-8
G9
HE-9
H1
HE-1
H2
HE-2
H3
HE-2
H4
HE-4
H5
HE-5
H6
HE-6
H7
HE-7
H8
HE-8
H9
HE-9
I1
HE-1
I2
HE-2
I3
HE-2
I4
HE-4
I5
HE-5
I6
HE-6
I7
HE-7
I8
HE-8
I9
HE-9
J1
HE-1
J2
HE-2
J3
HE-2
J4
HE-4
J5
HE-5
J6
HE-6
J7
HE-7
J8
HE-8
J9
HE-9
K1
HE-1
K2
HE-2
K3
HE-2
K4
HE-4
K5
HE-5
K6
HE-6
K7
HE-7
K8
HE-8
K9
HE-9
L1
HE-1
L2
HE-2
L3
HE-2
L4
HE-4
L5
HE-5
L6
HE-6
L7
HE-7
L8
HE-8
L9
HE-9
7. An electroluminescent device, comprising a compound of formula I according to claim 1 .
8. Electroluminescent device according to claim 7 , 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.
9. A process for the preparation of compounds of the formula I according to claim 1 , which comprises reacting a derivative of formula
wherein
R 100 stands for halogen,
with boronic acid derivative E-Ar, E having the meaning of
wherein a is 2 or 3, Ar has the meaning of Z 1 ,
in the presence of an allylpalladium catalyst, wherein A, Z 1 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and x are as defined in claim 1 .
10. A compound of formula
wherein
R 1 and R 4 are independently of each other hydrogen, F, 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, F, 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, CN, 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 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, 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, F, 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′ 7 is 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, —N(C 6 -C 18 aryl) 2 , 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 11 and R 12 , and/or R 14 and R 16 , 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 121 ), or NR 17 , wherein R 17 is as defined above, R 195 , 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 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
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 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 is C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—,
R 28 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 29 is C 6 -C 18 aryl; C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—,
R 30 and R 31 are independently of each other C 1 -C 18 alkyl, C 6 -C 18 aryl, or C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl, and
R 32 is C 1 -C 18 alkyl, C 6 -C 18 aryl, or C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl, and
Z 1 and Z 2 are independently of each other a group
or
Z 1 and Z 2 are both
wherein R 5″ is hydrogen, or has the meaning of R 6 ,
R 6″ , R 7″ , R 8″ and R 9″ are independently of each other C 6 -C 18 aryl; which may optionally be substituted by G; or C 2 -C 20 heteroaryl, which may optionally be substituted by G,
X 3 represents O, S or N—R 121′ ,
X 9 represents O, S or N—R 121′ ,
Q 1 and Q 2 represents atoms necessary for forming a carbocyclic aromatic, or heterocyclic aromatic ring, which can optionally be condensed with other ring(s) to form a condensed ring, and/or can optionally be substituted by G,
R 121′ is C 6 -C 18 aryl; or C 2 -C 20 heteroaryl; which can optionally be 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—;
R 116 , 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 126 , or substituents R 116 , R 116′ , R 117 and R 117′ , which are adjacent to each other, can form a ring,
R 126 and R 127 are independently of each other C 6 -C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 1 -C 18 alkyl which is interrupted by —O—,
R 120 , R 123 , R 124 and R 125 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, which can optionally be substituted by G, C 2 -C 20 heteroaryl, which can optionally be 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,
R 128 is H, CN, 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, which can optionally be substituted by G, C 2 -C 20 heteroaryl, which can optionally be 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,
L 1 is a single bond, —(CR 47 ═CR 48 ) m2 —, —(Ar 3 ) m3 —, —[Ar 3 (Y 1 ) m1 ] m4 —, —[(Y 1 ) m1 Ar 3 ] m4 —, or —[Ar 3 (Y 2 ) m1 Ar 4 ] m4 —, wherein
Y 1 is —(CR 47 ═CR 48 )—,
Y 2 is NR 49 , O, S, C═O, C(═O)O, wherein R 49 is H; C 6 -C 18 aryl which can optionally be 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 47 and R 48 are independently of each other hydrogen, fluorine, C 1 -C 20 alkyl, or C 6 -C 24 aryl, which can optionally be substituted by G,
m1 is an integer of 1 to 10, m2 is an integer of 1 to 10, m3 is an integer of 1 to 5, m4 is an integer of 1 to 5,
Ar 3 and Ar 4 are independently of each other arylen, or heteroarylen, which can optionally be substituted,
X 4 , X 5 and X 6 are independently of each other N, or CH, with the proviso that at least one of the substituents X 4 , X 5 and X 6 are N,
Ar 1 and Ar 2 are independently of each other C 6 -C 24 aryl, which can optionally be substituted by G, or C 2 -C 20 heteroaryl, which can optionally be substituted by G, wherein D, E and G are as defined above.