Diketopyrrolopyrrole polymers for use in organic semiconductor devices

1. A polymer comprising one or more (repeating) unit(s) of the formula (I),

wherein a is 1, 2, or 3, a′ is 0, 1, 2, or 3; b is 0, 1, 2, or 3; b′ is 0, 1, 2, or 3; c is 0, 1, 2, or 3; c′ is 0, 1, 2, or 3; d is 0, 1, 2, or 3; d′ is 0, 1, 2, or 3; with the proviso that b′ is not 0, if a′ is 0;

R 1 and R 2 may be the same or different and are selected from hydrogen, a C 1 -C 100 alkyl group, —COOR 103 , a C 1 -C 100 alkyl group which is substituted by one or more halogen atoms, hydroxyl groups, nitro groups, —CN, or C 6 -C 18 aryl groups and/or interrupted by —O—, —COO—, —OCO—, or —S—; a C 7 -C 100 arylalkyl group, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy; a carbamoyl group, C 5 -C 12 cycloalkyl, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy; a C 6 -C 24 aryl group, in particular phenyl or 1- or 2-naphthyl which can be substituted one to three times with C 1 -C 8 alkyl, C 1 -C 8 thioalkoxy, and/or C 1 -C 8 alkoxy, or pentafluorophenyl,

Ar 1 and Ar 1′ are independently of each other an annulated (aromatic) heterocyclic ring system, containing at least one thiophene ring, which are groups of formula

which may be optionally substituted by one, or more groups,

R 3 and R 3′ are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C 7 -C 25 arylalkyl, or C 1 -C 25 alkoxy;

R 4 , R 4′ , R 5 , R 5′ , R 6 and R 6′ are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C 7 -C 25 arylalkyl, or C 1 -C 25 alkoxy;

R 114 is C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms,

R 7 , R 7′ , R 9 and R 9′ are independently of each other hydrogen, C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms; or C 7 -C 25 arylalkyl,

R 8 and R 8′ are independently of each other hydrogen, 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; or C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C 7 -C 25 arylalkyl,

R 11 and R 11′ are independently of each other C 1 -C 25 alkyl group, especially a C 1 -C 8 alkyl group, C 7 -C 25 arylalkyl, or a phenyl group, which can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy;

R 12 and R 12′ are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, C 1 -C 25 alkoxy, C 7 -C 25 arylalkyl, or

 wherein R 13 is a C 1 -C 10 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group,

Ar 2 , Ar 2′ , Ar 3 , Ar 3′ , Ar 4 and Ar 4′ have the meaning of Ar 1 , or are independently of each other

 wherein

one of X 3 and X 4 is N and the other is CR 99 ,

R 99 , R 104 and R 104′ are independently of each other hydrogen, halogen, especially F, or a C 1 -C 25 alkyl group, especially a C 4 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C 7 -C 25 arylalkyl, or a C 1 -C 25 alkoxy group,

R 105 , R 105′ , R 106 and R 106′ are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C 7 -C 25 arylalkyl, or C 1 -C 18 alkoxy,

R 107 is C 7 -C 25 arylalkyl, 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; C 1 -C 18 alkyl which is interrupted by —O—, or —S—; or —COOR 103 ; R 103 is C 1 -C 50 alkyl, especially C 4 -C 25 alkyl;

R 108 and R 109 are independently of each other H, C 1 -C 25 alkyl, C 1 -C 25 alkyl which is substituted by E and/or interrupted by D, C 7 -C 25 arylalkyl, 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 108 and R 109 together form a group of formula ═CR 110 R 111 , wherein

R 110 and R 111 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 108 and R 109 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, or C 7 -C 25 aralkyl,

D is —CO—, —COO—, —S—, —O—, or —NR 112 ,

E is C 1 -C 8 thioalkoxy, C 1 -C 8 alkoxy, CN, —NR 112 R 113 , —CONR 112 R 113 , or halogen,

G is E, or C 1 -C 18 alkyl, and

R 112 and R 113 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—.

2. The polymer according to claim 1 , comprising one or more (repeating) unit(s) of the formula

wherein

R 1 is a C 8 -C 36 alkyl group,

R 3 is hydrogen, halogen, C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C 7 -C 25 aralkyl, or C 1 -C 25 alkoxy;

R 4 , R 4′ , R 5 , R 5′ and R 6 are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C 7 -C 25 aralkyl, or C 1 -C 25 alkoxy;

R 7 , R 7′ , R 9 and R 9′ are independently of each other hydrogen, C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, or C 7 -C 25 aralkyl,

R 8 is C 7 -C 25 aralkyl, 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; or C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, and

R 12 and R 12′ are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, C 1 -C 25 alkoxy,

wherein R 13 is a C 1 -C 10 alkyl group, or a tri(C 1 -C 8 alkyl)silyl group.

3. The polymer according to claim 1 , comprising (repeating) unit(s) of the formula * A * and * COM 1 * (II), wherein

A is a repeating unit of formula (I), and

—COM 1 - is a repeating unit, which is selected from a group of formula Ar 1 , such as, for example,

 wherein

one of X 5 and X 6 is N and the other is CR 14 ,

R 14 , R 14′ , R 17 and R 17′ are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C 7 -C 25 aralkyl, or C 1 -C 25 alkoxy;

R 18 and R 18′ independently of each other hydrogen, halogen, C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C 7 -C 25 aralkyl, or C 1 -C 25 alkoxy;

R 19 is hydrogen, C 7 -C 25 aralkyl, 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; or C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms;

R 20 and R 20′ are independently of each other hydrogen, C 7 -C 25 aralkyl, C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, and Ar 1 is as defined in claim 1 .

4. The polymer according to claim 3 , wherein A is a repeating unit of formula (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii), (Ij), (Ik), (Il), (Im), (In), (Io), (Ip), (Iq), (Ir), (Is), (It), (Iu) or (Iv) as defined in claim 3 .

5. The polymer according to claim 3 , comprising one or more (repeating) unit(s) of the formula

wherein

R 1 is a C 8 -C 36 alkyl group,

R 3 is hydrogen, halogen, C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C 7 -C 25 aralkyl, or C 1 -C 25 alkoxy;

R 4 , R 4′ and R5 are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms, C 7 -C 25 aralkyl, or C 1 -C 25 alkoxy;

R 7 , R 7′ , R 9 and R 9′ are independently of each other hydrogen, C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms; or C 7 -C 25 aralkyl,

R 8 is C 7 -C 25 aralkyl, 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; or C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms;

R 19 is C 7 -C 25 aralkyl, 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; or C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms,

one of X 5 and X 6 is N and the other is CR 14 ,

R 14 , R 14′ , R 17 and R 17′ are independently of each other hydrogen, halogen, C 1 -C 25 alkyl, C 1 -C 25 alkoxy, especially C 4 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C 7 -C 25 aralkyl,

R 18 and R 18′ independently of each other hydrogen, halogen, C 1 -C 25 alkyl, especially C 4 -C 25 alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C 7 -C 25 aralkyl, or C 1 -C 25 alkoxy.