Dibenzofurane polymers for electroluminiscent devices

1. Electroluminescent composition comprising a homopolymer of formula III

wherein

n ranges from 2 to 10000;

L is CH 2 , CO or a direct bond;

R 9 , R 11 , R 13 , R 14 , are selected from H, C 1 -C 18 alkyl, halogen, 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 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, SiRR′R″,

GeRR′R″, POAr 2 , PAr 2 , or is —CO—R 28 ;

each of the residues R 9″ is independently selected from those defined for R 9 ,

Rx is H or methyl,

SP is a divalent organic spacer,

X10 is o or 1;

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 3 -C 12 cycloalkyl, C 2 -C 18 alkyl which is interrupted by D, C 1 -C 18 perfluoroalkyl, 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 arylalkyl; C 3 -C 12 cycloalkyl; C 6 -C 18 aryl or C 6 -C 18 arylalkyl which is substituted by C 1 -C 18 alkyl and/or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; or C 2 -C 8 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 arylalkyl; C 6 -C 18 aryl or C 6 -C 18 arylalkyl which is substituted by C 1 -C 18 alkyl and/or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; C 3 -C 12 cycloalkyl; or C 2 -C 18 alkyl which is interrupted by —O—;

R 29 is H; C 6 -C 18 aryl; C 6 -C 18 arylalkyl; C 6 -C 18 aryl or C 6 -C 18 arylalkyl which is substituted by C 1 -C 18 alkyl and/or C 1 -C 18 alkoxy; C 1 -C 18 alkyl; C 2 -C 18 alkylcarbonyl; C 3 -C 12 cycloalkyl; or C 2 -C 18 alkyl or C 2 -C 8 alkylcarbonyl which is interrupted by —O—;

R 30 and R 31 are independently of each other C 1 -C 18 alkyl, C 3 -C 12 cycloalkyl, 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,

R, R′ and R″ independently are selected from C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 5 -C 10 aryl, C 3 -C 12 cycloalkyl; and

Ar independently is selected from C 5 -C 10 aryl, or C 5 -C 10 aryl which is substituted by C 1 -C 18 alkyl;

and

a luminescent component selected from phosphorescent metal complexes and fluorescent dopants.

2. Electroluminescent composition of claim 1 , wherein n ranges from 5 to 5000;

X10 is 0;

R 9 , R 9″ , R 11 , R 13 , R 14 , are selected from H, C 1 -C 8 alkyl, fluoro, C 1 -C 8 alkyl which is substituted by E, C 2 -C 18 alkyl which is interrupted by D, phenyl, phenyl which is substituted by G, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 1 -C 8 alkoxy, C 1 -C 8 alkoxy which is substituted by E, C 2 -C 18 alkoxy which is interrupted by D, C 7 -C 25 phenylalkyl, SiRR′R″, GeRR′R″, POAr 2 , PAr 2 , or is —CO—R 28 ;

D is —CO—; —COO—; —S—; —SO—; —SO 2 —; —O—; —NR 25 —; —SiR 3 OR 31 —; —POR 32 —; and

E is —OR 29 ; —NR 25 R 26 ; —COR 28 ; —COOR 27 ; —CONR 25 R 26 ; —CN; or halogen;

G is E, C 1 -C 8 alkyl, cyclohexyl, C 2 -C 18 alkyl which is interrupted by D, C 1 -C 8 perfluoroalkyl, C 1 -C 18 alkoxy which is substituted by E, C 2 -C 18 alkoxy which is interrupted by D, wherein

R 25 and R 26 are independently of each other H; phenyl; C 7 -C 12 phenylalkyl; cyclohexyl; phenyl or C 7 -C 12 phenylalkyl which is substituted by C 1 -C 8 alkyl or C 1 -C 8 alkoxy; C 1 -C 18 alkyl; or C 2 -C 18 alkyl which is interrupted by —O—; or

R 25 and R 26 together form a five or six membered ring selected from

R 27 and R 28 are independently of each other H; phenyl; C 7 -C 12 phenylalkyl; phenyl or C 7 -C 12 phenylalkyl which is substituted by C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy; C 1 -C 8 alkyl; cyclohexyl; or C 2 -C 18 alkyl which is interrupted by —O—;

R 29 is H; phenyl; C 7 -C 12 phenylalkyl; phenyl or C 7 -C 12 phenylalkyl which is substituted by C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy; C 1 -C 8 alkyl; C 2 -C 8 alkylcarbonyl; cyclohexyl; or C 2 -C 18 alkyl or C 2 -C 18 alkylcarbonyl which is interrupted by —O—;

R 30 and R 31 are independently of each other C 1 -C 8 alkyl, phenyl, or phenyl which is substituted by C 1 -C 8 alkyl, and

R 32 is C 1 -C 8 alkyl, phenyl, or phenyl which is substituted by C 1 -C 8 alkyl,

R, R′ and R″ independently are selected from C 1 -C 6 alkyl, phenyl, cyclopentyl, cyclohexyl; and

Ar is phenyl or phenyl substituted by C 1 -C 8 alkyl.

3. Electroluminescent composition according to claim 1 containing 10 to 1000 structural units of the formula, wherein

X10 is 0;

any of R 9 , R 9″ , R 11 , R 13 , R 14 , independently is selected from H, C 1 -C 8 alkyl, fluoro, C 1 -C 8 alkyl which is substituted by E, C 2 -C 18 alkyl which is interrupted by D, phenyl, phenyl which is substituted by G, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 1 -C 8 alkoxy, C 1 -C 8 alkoxy which is substituted by E, C 2 -C 18 alkoxy which is interrupted by D, C 7 -C 25 phenylalkyl, SiRR′R″, GeRR′R″, POAr 2 , PAr 2 , or is —CO—R 28 ;

D is —CO—; —COO—; —O—; —NR 25 —; —SiR 3 OR 31 —; and

E is −OR 29 ; —NR 25 R 26 ; —COR 28 ; —COOR 27 ; —CONR 25 R 26 ; or fluoro;

G is E or C 1 -C 8 alkyl;

R 25 and R 26 are independently of each other H; C 1 -C 8 alkyl; cyclohexyl;

R 27 and R 28 are independently of each other H; phenyl; benzyl; phenyl or benzyl which is substituted by C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy; C 1 -C 8 alkyl;

R 29 is H; phenyl; benzyl; phenyl or benzyl which is substituted by C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy; C 1 -C 8 alkyl; acetyl; cyclohexyl; or C 2 -C 12 alkyl which is interrupted by —O—;

R 30 and R 31 are independently of each other methyl or phenyl, and

R, R′ and R″ independently are selected from methyl, ethyl, phenyl; and

Ar is phenyl.

4. Electroluminescent composition of claim 1 , wherein any of R 9 , R 9″ , R 11 , R 13 , R 14 , independently is selected from H, C 1 -C 8 alkyl, SiRR′R″.

5. Electroluminescent composition as defined in claim 1 , which comprises one or more further component(s)selected from electron transporters, hole transporters, inert polymers, viscosity modifiers, initiators, organic salts, and stabilizers.

6. An organic electronic device, comprising a layer of an electroluminescent material according to claim 1 .

7. A device according to claim 6 selected from stationary and mobile displays.

8. Homopolymer of the formula III′

wherein

n ranges from 5 to 10000;

at least one of the residues R 9 , R 9″ , R 11 , R 13 , R 14 is selected from C 1 -C 18 alkyl, halogen, 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 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, SiRR′R″, GeRR′R″, POAr 2 , PAr 2 , CO—R 28 ;

while the remaining residues may also be hydrogen;

D is —CO—; —COO—; —S—; —SO—; —SO 2 —; —O—; —NR 25 —; —SiR 3 OR 31 —; —POR 32 —; and

E is —OR 29 ; —NR 25 R 26 ; —COR 28 ; —COOR 27 ; —CONR 25 R 26 ; —CN; or halogen;

G is E, C 1 -C 8 alkyl, cyclohexyl, C 2 -C 18 alkyl which is interrupted by D, C 1 -C 8 perfluoroalkyl, C 2 -C 18 alkoxy which is substituted by E, C 2 -C 18 alkoxy which is interrupted by D, wherein

R 25 and R 26 are independently of each other H; phenyl; C 7 -C 12 phenylalkyl; cyclohexyl; phenyl or C 7 -C 12 phenylalkyl which is substituted by C 1 -C 8 alkyl or C 1 -C 8 alkoxy; C 1 -C 18 alkyl; or C 2 -C 18 alkyl which is interrupted by —O—; or

R 25 and R 26 together form a five or six membered ring selected from

R 27 and R 28 are independently of each other H; phenyl; C 7 -C 12 phenylalkyl; phenyl or C 7 -C 12 phenylalkyl which is substituted by C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy; C 1 -C 8 alkyl; cyclohexyl; or C 2 -C 18 alkyl which is interrupted by —O—;

R 29 is H; phenyl; C 7 -C 12 phenylalkyl; phenyl or C 7 -C 12 phenylalkyl which is substituted by C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy; C 1 -C 8 alkyl; C 2 -C 8 alkylcarbonyl; cyclohexyl; or C 2 -C 18 alkyl or C 2 -C 18 alkylcarbonyl which is interrupted by —O—;

R 39 and R 31 are independently of each other C 1 -C 8 alkyl, phenyl, or phenyl which is substituted by C 1 -C 8 alkyl, and

R 32 is C 1 -C 8 alkyl, phenyl, or phenyl which is substituted by C 1 -C 8 alkyl,

R, R′ and R″ independently are selected from C 1 -C 6 alkyl, phenyl, cyclopentyl, cyclohexyl; and

Ar is phenyl or phenyl substituted by C 1 -C 8 alkyl;

L is CH 2 , CO or a direct bond; Rx is H or methyl;

X10 is 0 or 1 and Sp is O, C 1 -C 4 alkylene-O, CH 2 —CHOH—CH 2 —O, COO, CONR22, C 1 -C 4 alkylene, or CH 2 CHOHCH 2 .

9. Compound of the formula V

wherein

at least one of the residues R 9 , R 9″ , R 11 , R 13 , R 14 is selected from halogen, C 2 -C 18 alkynyl, C 1 -C 18 alkoxy, SiRR′R″, GeRR′R″, POAr 2 , PAr 2 ;

R, R′ and R″ independently are selected from C 1 -C 6 alkyl, phenyl, cyclopentyl, cyclohexyl; and

Ar is phenyl or phenyl substituted by C 1 -C 8 alkyl;

L is CH 2 , CO or a direct bond; Rx is H or methyl;

X10 is 0 or 1 and Sp is O, C 1 -C 4 alkylene-O, CH 2 —CHOH—CH 2 —O, COO, CONR22, C 1 -C 4 alkylene, or CH 2 CHOHCH 2 .