Novel diketopyrrolopyrrole polymers

Abstract

The present invention relates to polymers comprising a repeating unit of the formula (I) and their use in electronic devices. The polymers according to the invention have excellent solubility in organic solvents and excellent film-forming properties. In addition, high charge carrier mobilities and high temperature stability of the emission color are observed, if the polymers according to the invention are used in polymer light emitting diodes (PLEDs).

1 . A polymer comprising a repeating unit of the formula 
       
         
           
           
               
               
           
         
       
       wherein
 Ar 1  and Ar 2  are independently of each other a C 6 -C 30 aryl group or a C 2 -C 26 heteroaryl group, which can optionally be substituted, 
 R 1  and R 2  are independently of each other a C 1 -C 25 alkyl group which can optionally be interrupted by one or more oxygen atoms, an allyl group which can optionally be substituted one to three times with C 1 -C 4 alkyl, a cycloalkyl group which can be optionally substituted one to three times with C 1 -C 8 alkyl or C 1 -C 8 alkoxy, a cycloalkyl group which can optionally be condensed one or two times by phenyl which phenyl can optionally be substituted one to three times with C 1 -C 4 -alkyl, halogen, nitro or cyano, an alkenyl group, a cycloalkenyl group, an alkynyl group, said C 1 -C 25 alkyl group, alkenyl group, or alkynyl group substituted partially or wholly by halogen, an aldehyde group, an ester group, a carbamoyl group, a ketone group, a silyl group, a siloxanyl group, Ar 3  or a group —CR 3 R 4 —(CH 2 ) g —Ar 3 , 
 wherein R 3  and R 4  independently from each other stand for hydrogen, fluorine, cyano or C 1 -C 4 alkyl which can be substituted by fluorine, chlorine or bromine, or phenyl which can be substituted one to three times with C 1 -C 4 alkyl, 
 Ar 3  stands for aryl or heteroaryl, and g stands for 0, 1, 2, 3 or 4. 
 
     
     
         2 . The polymer according to  claim 1 , wherein Ar 1  and Ar 2  are independently of each other 
       
         
           
           
               
               
           
         
         wherein R 38  stands for hydrogen, C 6 -C 10 aryl, C 7 -C 12 alkylaryl, C 7 -C 12 aralkyl, or C 1 -C 8 -alkyl. 
       
     
     
         3 . The polymer according to  claim 1 , wherein Ar 1  and Ar 2  are independently of each other 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein R 25 , R 26  and R 27  independently from each other stands for hydrogen, C 1 -C 25 alkyl, C 1 -C 25 alkoxy, —CR 11 R 12 —(CH 2 ) g —Ar 6 , cyano, NO 2 , halogen, —OR 29 , —NR 29 R 30 , —S(O) p R 31 , C 2 -C 8 heteroaryl, or C 8 -C 14 aryl which can be substituted one to three times with C 1 -C 8 alkyl or C 1 -C 8 alkoxy, 
         wherein R 29  and R 30  independently of each other stand for H, C 1 -C 25 -alkyl, C 5 -C 12 -cycloalkyl, —CR 11 R 12 -(CH 2 ) g -Ph, C 6 -C 24 aryl, or a saturated or unsaturated heterocyclic group comprising five to seven ring atoms, wherein the ring consists of carbon atoms and one to three hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, 
         R 31  stands for C 1 -C 25 alkyl, or C 8 -C 14 aryl, 
         R 28  stands for C 6 -C 30 arylene, 
         p stands for 0, 1, 2 or 3, g and h stands for 0, 1, 2, 3 or 4, 
         Ar 6  stands for phenyl or 1- or 2-naphthyl which can be substituted one to three times with C 1 -C 8 alkyl, C 1 -C 8 alkoxy, halogen, nitro, cyano or phenyl which can be substituted with C 1 -C 8 alkyl or C 1 -C 8 alkoxy one to three times, or —NR 23 R 24 , wherein R 23  and R 24  represent hydrogen, C 1 -C 25 -alkyl, C 5 -C 12 -cycloalkyl or C 6 -C 24 -aryl, and 
         R 11  and R 12  independently from each other stand for hydrogen, fluorine, cyano or C 1 -C 4 alkyl which can be substituted by fluorine, or phenyl which can be substituted one to three times with C 1 -C 4 alkyl, or 
       
       
         
           
           
               
               
           
         
       
       wherein
 R 29′  stands for H, C 1 -C 25 -alkyl, C 5 -C 12 -cycloalkyl, CR 11 R 12 (C 2 ) g -Ph, C 6 -C 24 aryl, 
 R 30′  stands for C 6 -C 30 arylene, or 
 R 29′  and R 30′  together with the nitrogen to which they are bonded form a group of formula 
 
       
         
           
           
               
               
           
         
         and g, R 11 , R 12 , R 25  and R 26  are as defined above. 
       
     
     
         4 . The polymer according to  claim 1 , comprising one or more repeating unit(s) Ar 3  which is selected from the group consisting of 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       wherein
 r is an integer from 1 to 10, q is an integer from 1 to 10, 
 s is an integer from 1 to 10, 
 R 6  and R 7  are independently of each other H, halogen, —CN, C 1 -C 8 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 17 , —C(═O)OR 17 , or —C(═O)NR 17 R 16 , 
 R 9  and R 19  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, 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 9  and R 10  together form a group of formula ═CR 100 R 101 , wherein R 100  and R 101  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 9  and R 19  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 17 , and R 16  and R 17  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, —OCOOR 67 , or halogen, 
 G is E, C 1 -C 18 alkyl, 
 R 63 , R 64 , R 65  and R 66  are independently of each other H; O 6 —C 18 aryl; C 6 -C 18 aryl which is substituted by C 1 -C 18 alkyl, 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; O 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; O 6 —C 18 aryl; C 6 -C 18 aryl, which is substituted by C 1 -C 18 alkyl, 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; 
 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       wherein
 R 41  can be the same or different at each occurrence 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—, —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 42  can be the same or different at each occurrence and is CN, 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 44  can be the same or different at each occurrence and are a hydrogen atom, 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 CN, or 
 two or more groups R 44 , which are in neighbourhood to each other, form a ring; 
 R 45  is H, 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 ; 
 m can be the same or different at each occurrence and is 0, 1, 2, or 3, n can be the same or different at each occurrence and is 0, 1, 2, or 3o is 1, 2, or 3, and u is 1, 2, 3, or 4; 
 A 1  is a C 6 -C 24 aryl group, a C 2 -C 30 heteroaryl group, which can be substituted by one or more non-aromatic groups R 41 , or NO 2 , 
 A 2  and A 3  are independently of each other 
 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       wherein R 6 ,
 R 7 , R 9  and R 10  are as defined above, 
 R 8  is H, C 1 -C 18 alkyl, C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, O 6 —O 24  aryl, or C 7 -C 25 aralkyl, 
 R 14  and R 15  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 E, or C 2 -C 20 heteroaryl, C 2 -C 20 heteroaryl which is substituted by E, wherein E and D are as defined above 
 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein R 41  and m and n are as defined above and 
         p is 0, 1, or 2; 
       
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       wherein
 X is O, S, or NR 45 , 
 R 43  is a hydrogen atom, 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 CN, or 
 two or more groups R 43  and/or R 44 , which are in neighbourhood to each other, form a ring; and A 1 , R 41 , R 42 , R 44 , R 45 , m, n, o and p are as defined above; 
 and repeating unit(s) -T- which is selected from the group consisting of 
 
       
         
           
           
               
               
           
         
       
       wherein
 X 1  is a hydrogen atom, or a cyano group, 
 R 41  can be the same or different at each occurrence 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—, —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; 
 n can be the same or different at each occurrence and is 0, 1, 2, or 3 and u is 1, 2, 3, or 4; 
 A 1  is a C 6 -C 24 aryl group, a C 2 -C 30 heteroaryl group, especially phenyl, naphthyl, anthryl, biphenylyl, 2-fluorenyl, phenanthryl, or perylenyl, which can be substituted by one or more non-aromatic groups R 41 . 
 
     
     
         5 . The polymer according to  claim 4 , wherein the polymer comprises a repeating unit of formula 
       
         
           
           
               
               
           
         
       
       wherein
 R 1  and R 2  are independently of each other a C 1 -C 25 alkyl group, which can be interrupted by one or more oxygen atoms, 
 R 6  and R 7  are as defined above and are especially H, halogen, CN, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, or C 6 -C 14 aryl, 
 A 1  is a C 6 -C 24 aryl group, a C 2 -C 30 heteroaryl group, which can be substituted by one or more non-aromatic groups R 41 , or NO 2 , and 
 Ar 1  and Ar 2  are independently of each other a group of formula 
 
       
         
           
           
               
               
           
         
         wherein R 6  is hydrogen, C 1 -C 18 alkyl, or C 1 -C 18 alkoxy, and R 32  is methyl, Cl, or OMe. 
       
     
     
         6 . The polymer according to  claim 1 , wherein the polymer is homopolymer comprising a repeating unit of formula 
       
         
           
           
               
               
           
         
       
       wherein
 R 1  and R 2  are independently of each other a C 1 -C 25 alkyl group, which can be interrupted by one or more oxygen atoms, and 
 Ar 1  and Ar 2  are independently of each other a group of formula 
 
       
         
           
           
               
               
           
         
       
       wherein R 6  is hydrogen, C 1 -C 18 alkyl, or C 1 -C 18 alkoxy, and R 32  is methyl, Cl, or OMe. 
     
     
         7 . The polymer according to  claim 1 , wherein the polymer comprises a repeating unit of formula 
       
         
           
           
               
               
           
         
       
       and a repeating unit [—Ar 3 —], wherein
 R 1  and R 2  are independently of each other a C 1 -C 25 alkyl group, which can be interrupted by one or more oxygen atoms, and Ar 1  and Ar 2  are independently of each other a group of formula 
 
       
         
           
           
               
               
           
         
         wherein —Ar 3 — is a group of formula 
       
       
         
           
           
               
               
           
         
       
       wherein
 R 6  is hydrogen, C 1 -C 18 alkyl, or C 1 -C 18 alkoxy, and R 32  is methyl, Cl, or OMe, and R 8  is H, C 1 -C 18 alkyl, or C 1 -C 18 alkyl which is substituted by E and/or interrupted by D, especially C 1 -C 18 alkyl which is interrupted by —O—, 
 
       wherein
 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, —OCOOR 67 , or halogen, 
 R 63 , R 64 , 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, 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, 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. 
 
     
     
         8 . The polymer according to  claim 1 , wherein the polymer is a terpolymer comprising a repeating unit of formula 
       
         
           
           
               
               
           
         
       
       a repeating unit of formula 
       
         
           
           
               
               
           
         
       
       and a repeating unit of formula 
       
         
           
           
               
               
           
         
       
       wherein
 R 1  and R 2  are independently of each other a C 1 -C 25 alkyl group, which can be interrupted by one or more oxygen atoms, and Ar 1  and Ar 2  are independently of each other a group of formula 
 
       
         
           
           
               
               
           
         
         R 6  and R 7  are independently of each other H, halogen, CN, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, or C 6 -C 14 aryl, 
         R 41  is Cl, F, CN, N(R 45 ) 2 , C 1 -C 18 alkyl, C 1 -C 18 alkoxy, or C 6 -C 14 aryl, wherein 
         R 45  is H, a C 1 -C 25 alkyl group, or a C 1 -C 25 alkoxy group, and n is 0, 1, or 2. 
       
     
     
         9 . The polymer according to  claim 1 , wherein the polymer is a polymer of formula 
       
         
           
           
               
               
           
         
       
       wherein
 R 1 , R 2 , Ar 1 , Ar 2  and Ar 3  are as defined in  claim 1 , 
 T is selected from the group consisting of 
 
       
         
           
           
               
               
           
         
       
       wherein
 X 1  is a hydrogen atom, or a cyano group, 
 R 41  can be the same or different at each occurrence 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—, —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; 
 n can be the same or different at each occurrence and is 0, 1, 2, or 3 and u is 1, 2, 3, or 4; 
 A 1  is a C 6 -C 24 aryl group, a C 2 -C 30 heteroaryl group, especially phenyl, naphthyl, anthryl, biphenylyl, 2-fluorenyl, phenanthryl, or perylenyl, which can be substituted by one or more non-aromatic groups R 41 , 
 a is 1, 
 b is 0, or 1, 
 c is 0.005 to 1, 
 d is 0, or 1, 
 e is 0, or 1, wherein e is not 1, if d is 0, 
 f is 0.995 to 0, wherein the sum of c and f is 1. 
 
     
     
         10 . An electronic device or a component therefore, comprising the polymer according to  claim 1 . 
     
     
         11 . An electronic device according to  claim 10 , wherein the device comprises an electroluminescent device. 
     
     
         12 . An electronic device according to  claim 11 , wherein the electroluminescent device comprises
 (a) a charge injecting layer for injecting positive charge carriers,   (b) a charge injecting layer for injecting negative charge carriers,   (c) a light-emissive layer located between the layers (a) and (b) comprising the polymer comprising a repeating unit of formula I.   
     
     
         13 . PLEDs, organic integrated circuits (O—ICs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic solar cells (O—SCs), or organic laser diodes comprising one or more of the polymers according to  claim 1 . 
     
     
         14 . The polymer according to  claim 1 , wherein Ar 3  stands for phenyl or 1- or 2-naphthyl which phenyl or 1- or 2-naphthyl can be substituted one to three times with C 1 -C 8 alkyl and/or C 1 -C 8 alkoxy. 
     
     
         15 . The polymer according to  claim 3 , wherein the C 6 -C 30 arylene of R 28′  or R 30′  is independently of the other 
       
         
           
           
               
               
           
         
       
     
     
         16 . The polymer according to  claim 15 , wherein Ar 1  and Ar 2  are independently of each other 
       
         
           
           
               
               
           
         
       
     
     
         17 . The polymer according to  claim 5 , wherein the polymer comprises a repeating unit of formula