Benzothienothiophene isoindigo polymers
Polymers comprising at least one unit of formula (1) and their use as semiconducting materials.
1. A polymer comprising at least one unit of formula (1):
wherein
R 1 is at each occurrence selected from the group consisting of H, C 1-100 -alkyl, C 2-100 -alkenyl, C 2-100 -alkynyl, C 5-12 -cycloalkyl, C 6-18 -aryl, a 5 to 20 membered heteroaryl, C(O)—C 1-100 -alkyl, C(O)—C 5-12 -cycloalkyl and C(O)—OC 1-100 -alkyl,
wherein
C 1-100 -alkyl, C 2-100 -alkenyl and C 2-100 -alkynyl can be substituted with one to forty substituents independently selected from the group consisting of C 5-8 cycloalkyl, C 6-14 -aryl, 5 to 14 membered heteroaryl, OR a , OC(O)—R a , C(O)—OR a , C(O)—R a , NR a R b , NR a —C(O)R b , C(O)—NR a R b , N[C(O)R a ][C(O)R b ], SR a , Si(R Sia )(R Sib )(R Sic ), —O—Si(R Sia )(R Sib )(R Sic ), halogen, CN, and NO 2 ; and at least two CH 2 -groups, but not adjacent CH 2 -groups, of C 1-100 -alkyl, C 2-100 -alkenyl and C 2-100 -alkynyl can be replaced by O or S,
C 5-12 -cycloalkyl can be substituted with one to six substituents independently selected from the group consisting of C 1-60 -alkyl, C 2-60 -alkenyl, C 2-60 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, 5 to 14 membered heteroaryl, OR a , OC(O)—R a , C(O)—OR a , C(O)—R a , NR a R b , NR a —C(O)R b , C(O)—NR a R b , N[C(O)R a ][C(O)R b ], SR a , Si(R Sia )(R Sib )(R Sic ), —O—Si(R Sia )(R Sib )(R Sic ), halogen, CN, and NO 2 ; and one or two CH 2 -groups, but not adjacent CH 2 -groups, of C 5-12 -cycloalkyl can be replaced by O, S, OC(O), CO, NR a or NR a —CO,
C 6-18 -aryl and 5 to 20 membered heteroaryl can be substituted with one to six substituents independently selected from the group consisting of C 1-60 -alkyl, C 2-60 -alkenyl, C 2-60 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, 5 to 14 membered heteroaryl, OR a , OC(O)—R a , C(O)—OR a , C(O)—R a , NR a R b , NR a —C(O)R b , C(O)—NR a R b , N[C(O)R a ][C(O)R b ], SR a , Si(R Sia )(R Sib )(R Sic ), —O—Si(R Sia )(R Sib )(R Sic ), halogen, CN, and NO 2 ,
wherein
R a and R b are independently selected from the group consisting of H, C 1-60 -alkyl, C 2-60 -alkenyl, C 2-60 -alkynyl, C 5-8 cycloalkyl, C 6-14 -aryl and 5 to 14 membered heteroaryl,
R Sia , R Sib and R Sic are independently selected from the group consisting of H, C 1-60 -alkyl, C 2-60 -alkenyl, C 2-60 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, 5 to 14 membered heteroaryl, O—C 1-60 -alkyl, O—C 2-60 -alkenyl, O—C 2-60 -alkynyl, O—C 5-8 -cycloalkyl, O—C 6-14 -aryl, O-5 to 14 membered heteroaryl, —[O—SiR Sid R Sie ] o —R Sif , NR 5 R 6 , halogen and O—C(O)—R 5 ,
wherein
o is an integer from 1 to 50,
R Sid , R Sie , R Sif independently selected from the group consisting of H, C 1-60 -alkyl, C 2-60 -alkenyl, C 2-60 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, 5 to 14 membered heteroaryl, O—C 1-60 -alkyl, O—C 2-60 -alkenyl, O—C 2-60 -alkynyl, O—C 5-8 -cycloalkyl, O—C 6-14 -aryl, O-5 to 14 membered heteroaryl, —[O—SiR Sig R Sih ] p —R Sii , NR 50 R 60 , halogen and O—C(O)—R 50 ;
wherein
p is an integer from 1 to 50,
R Sig , R Sih , R Sii are independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, O—C 1-30 -alkyl, O—C 2-30 -alkenyl, O—C 2-30 -alkynyl, O—C 5-6 -cycloalkyl, O—C 6-10 -aryl, O-5 to 10 membered heteroaryl, O—Si(CH 3 ) 3 , NR 500 R 600 , halogen and O—C(O)—R 500 ,
R 5 , R 6 , R 50 , R 60 , R 500 and R 600 are independently selected from the group consisting of H, C 1-60 -alkyl, C 2-60 -alkenyl, C 2-60 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, and 5 to 14 membered heteroaryl,
C 1-60 -alkyl, C 2-60 -alkenyl and C 2-60 -alkynyl can be substituted with one to twenty substituents selected from the group consisting of C 5-6 -cycloalkyl, C 6-10 -aryl, OR c , OC(O)—R c , C(O)—OR c , C(O)—R c , NR c R d , NR c —C(O)R d , C(O)—NR c R d , N[C(O)R c ][C(O)R d ], SR c , Si(R Sij )(R Sik )(R Sil ), —O—Si(R Sij )(R Sik )(R Sil ), halogen, CN, and NO 2 ; and at least two CH 2 -groups, but not adjacent CH 2 -groups, of C 1-60 -alkyl, C 2-60 -alkenyl and C 2-60 -alkynyl can be replaced by O or S,
C 5-8 -cycloalkyl can be substituted with one to five substituents selected from the group consisting of C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, OR c , OC(O)—R c , C(O)—OR c , C(O)—R c , NR c R d , NR c —C(O)R d , C(O)—NR c R d , N[C(O)R c ][C(O)R d ], SR c , Si(R Sij )(R Sik )(R Sil ), —O—Si(R Sij )(R Sik )(R Sil ), halogen, CN, and NO 2 ; and one or two CH 2 -groups, but not adjacent CH 2 -groups, of C 5-8 -cycloalkyl can be replaced by O, S, OC(O), CO, NR c or NR c —CO,
C 6-14 -aryl and 5 to 14 membered heteroaryl can be substituted with one to five substituents independently selected from the group consisting of C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, OR c , OC(O)—R c , C(O)—OR c , C(O)—R c , NR c R d , NR c —C(O)R d , C(O)—NR c R d , N[C(O)R c ][C(O)R d ], SR c , Si(R Sij )(R Sik )(R Sil ), —O—Si(R Sij )(R Sik )(R Sil ), halogen, CN and NO 2 ;
wherein
R c and R d are independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl and C 2-30 -alkynyl,
R Sij , R Sik and R Sil are independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, O—C 1-30 -alkyl, O—C 2-30 -alkenyl, O—C 2-30 -alkynyl, O—C 5-6 -cycloalkyl, O—C 6-10 -aryl, O-5 to 10 membered heteroaryl, —[O—SiR Sim R Sin ] q —R Sio , NR 7 R 8 , halogen, and O—C(O)—R 7 ,
wherein
q is an integer from 1 to 50,
R Sim , R Sin , R Sio are independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, O—C 1-30 -alkyl, O—C 2-30 -alkenyl, O—C 2-30 -alkynyl, O—C 5-6 -cycloalkyl, O—C 6-10 -aryl, O-5 to 10 membered heteroaryl, —[O—SiR Sip R Siq ] r —R Sir , NR 70 R 80 , halogen, and O—C(O)—R 70 ;
wherein
r is an integer from 1 to 50,
R Sip , R Siq , R Sir are independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, O—C 1-30 -alkyl, O—C 2-30 -alkenyl, O—C 2-30 -alkynyl, O—C 5-6 -cycloalkyl, O—C 6-10 -aryl, O-5 to 10 membered heteroaryl, O—Si(CH 3 ) 3 , NR 700 R 800 , halogen and O—C(O)—R 700 ,
R 7 , R 8 , R 70 , R 80 , R 700 and R 800 are independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, and 5 to 10 membered heteroaryl,
C 1-30 -alkyl, C 2-30 -alkenyl and C 2-30 -alkynyl can be substituted with one to ten substituents selected from the group consisting of halogen, CN and NO 2 ,
R 2 is at each occurrence selected from the group consisting of hydrogen, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-12 -cycloalkyl, C 6-18 -aryl, 5 to 20 membered heteroaryl, OR 21 , OC(O)—R 21 , C(O)—OR 21 , C(O)—R 21 , NR 21 R 22 , NR 21 —C(O)R 22 , C(O)—NR 21 R 22 , N[C(O)R 21 ][C(O)R 22 ], SR 21 , halogen, CN, SiR Sis R Sit R Siu and OH,
wherein
R 21 and R 22 are independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-12 -cycloalkyl, C 6-18 -aryl and 5 to 20 membered heteroaryl, and
C 1-30 -alkyl, C 2-30 -alkenyl and C 2-30 -alkynyl can be substituted with one to ten substituents independently selected from the group consisting of C 5-8 -cycloalkyl, C 6-14 -aryl, 5 to 14 membered heteroaryl, OR e , OC(O)—R e , C(O)—OR e , C(O)—R e , NR e R f , NR e —C(O)R f , C(O)—NR e R f , N[C(O)R e ][C(O)R f ], SR e , halogen, CN, SiR Sis R Sit R Siu and NO 2 ; and at least two CH 2 -groups, but not adjacent CH 2 -groups, of C 1-30 -alkyl, C 2-30 -alkenyl and C 2-30 -alkynyl can be replaced by O or S,
C 5-12 -cycloalkyl can be substituted with one to six substituents independently selected from the group consisting of C 1-20 -alkyl, C 2-20 -alkenyl and C 2-20 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, 5 to 14 membered heteroaryl, OR e , OC(O)—R e , C(O)—OR e , C(O)—R e , NR e R f , NR e —C(O)R f , C(O)—NR e R f , N[C(O)R e ][C(O)R f ], SR e , halogen, CN, SiR Sis R Sit R Siu and NO 2 ; and one or two CH 2 -groups, but not adjacent CH 2 -groups, of C 5-12 -cycloalkyl can be replaced by O, S, OC(O), CO, NR e or NR e —CO,
C 6-18 -aryl and 5 to 20 membered heteroaryl can be substituted with one to six substituents independently selected from the group consisting of C 1-20 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, 5 to 14 membered heteroaryl, OR e , OC(O)—R e , C(O)—OR e , C(O)—R e , NR e R f , NR e —C(O)R f , C(O)—NR e R f , N[C(O)R e ][C(O)R f ], SR e , halogen, CN, SiR Sis R Sit R Siu and NO 2 ,
wherein
R Sis , R Sit , R Siu are independently from each other selected from the group consisting of H, C 1-20 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-6 -cycloalkyl, phenyl and O—Si(CH 3 ) 3 ,
R e and R f are independently selected from the group consisting of H, C 1-20 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, and 5 to 14 membered heteroaryl,
wherein
C 1-20 -alkyl, C 2-20 -alkenyl and C 2-20 -alkynyl can be substituted with one to five substituents selected from the group consisting of C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR g , OC(O)—R g , C(O)—OR g , C(O)—R g , NR g R h , NR g —C(O)R h , C(O)—NR g R h , N[C(O)R g ][C(O)R h ], SR g , halogen, CN, and NO 2 ;
C 5-8 -cycloalkyl can be substituted with one to five substituents selected from the group consisting of C 1-10 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR g , OC(O)—R g , C(O)—OR g , C(O)—R g , NR g R h , NR g —C(O)R h , C(O)—NR g R h , N[C(O)R g ][C(O)R h ], SR g , halogen, CN, and NO 2 ;
C 6-4 -aryl and 5 to 14 membered heteroaryl can be substituted with one to five substituents independently selected from the group consisting of C 1-10 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR g , OC(O)—R g , C(O)—OR g , C(O)—R g , NR g R h , NR g —C(O)R h , C(O)—NR g R h , N[C(O)R g ][C(O)R h ], SR g , halogen, CN, and NO 2 ;
wherein
R g and R h are independently selected from the group consisting of H, C 1-10 -alkyl, C 2-10 -alkenyl and C 2-10 -alkynyl,
wherein
C 1-10 -alkyl, C 2-10 -alkenyl and C 2-10 -alkynyl can be substituted with one to five substituents selected from the group consisting of halogen, CN and NO 2 ,
n is 0, 1, 2 or 3,
m is 0, 1, 2 or 3,
with the proviso that at least one of n and m is not 0,
and
L 1 and L 2 are independently from each other and at each occurrence selected from the group consisting of
2. The polymer of claim 1 , wherein
R 1 is at each occurrence selected from the group consisting of C 1-100 -alkyl, C 2-100 -alkenyl and C 2-100 -alkynyl,
wherein
C 1-100 -alkyl, C 2-100 -alkenyl and C 2-100 -alkynyl can be substituted with one to forty substituents independently selected from the group consisting of C 5-8 -cycloalkyl, C 6-14 -aryl, 5 to 14 numbered heteroaryl, OR a , OC(O)—R a , C(O)—OR a , C(O)—R a , NR a —C(O)R b , C(O)—NR a R b , SR a , Si(R Sia )(R Sib )(R Sic ), —O—Si(R Sia )(R Sib )(R Sic ), halogen, and CN; and at least two CH 2 -groups, but not adjacent CH 2 -groups, of C 1-100 -alkyl, C 2-100 -alkenyl and C 2-100 -alkynyl can be replaced by O or S,
wherein
R a and R b are independently selected from the group consisting of H, C 1-60 -alkyl, C 2-60 -alkenyl, C 2-60 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl and 5 to 14 membered heteroaryl,
R Sia , R Sib and R Sic are independently selected from the group consisting of H, C 1-60 -alkyl, C 2-60 -alkenyl, C 2-60 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, —[O—SiR Sid R Sic ] o —R Sif ,
wherein
o is an integer from 1 to 50,
R Sid , R Sie and R Sif are independently selected from the group consisting of H, C 1-60 -alkyl, C 2-60 -alkenyl, C 2-60 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, —[O—SiR Sig R Sih ] p —R Sii ,
wherein
p is an integer from 1 to 50,
R Sig R Sih , R Sii are independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, O—Si(CH 3 ) 3 ,
R 5 , R 6 , R 50 , R 60 , R 500 and R 600 are independently selected from the group consisting of H, C 1-60 -alkyl, C 2-60 -alkenyl, C 2-60 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, and 5 to 14 membered heteroaryl,
C 1-60 -alkyl, C 2-60 -alkenyl and C 2-60 -alkynyl can be substituted with one to twenty substituents selected from the group consisting of C 5-6 -cycloalkyl, C 6-10 -aryl, OR c , OC(O)—R c , C(O)—OR c , C(O)—R c , NR c —C(O)R d , C(O)—NR c R d , SR c , Si(R Sij )(R Sik )(R Sil ), —O—Si(R Sij) (R Sik )(R Sil ), halogen, and CN; and at least two CH 2 -groups, but not adjacent CH 2 -groups, of C 1-60 -alkyl, C 2-60 -alkenyl and C 2-60 -alkynyl can be replaced by O or S,
C 5-8 -cycloalkyl can be substituted with one to five substituents selected from the group consisting of C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, OR c , OC(O)—R c , C(O)—OR c , C(O)—R c , NR c —C(O)R d , C(O)—NR c R d , SR c , Si(R Sij )(R Sik )(R Sil ), —O—Si(R Sij )(R Sik )(R Sil ), halogen, and CN; and one or two CH 2 -groups, but not adjacent CH 2 -groups, of C 5-8 -cycloalkyl can be replaced by O, S, OC(O), CO, NR c or NR c —CO,
C 6-14 -aryl and 5 to 14 membered heteroaryl can be substituted with one to five substituents independently selected from the group consisting of C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, OR c , OC(O)—R c , C(O)—OR c , C(O)—R c , NR c —C(O)R d , C(O)—NR c R d , SR c , Si(R Sij )(R Sik )(R Sil ), —O—Si(R Sij )(R Sik )(R Sil ), halogen, and CN;
wherein
R c and R d are independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl and C 2-30 -alkynyl,
R Sij , R Sik and R Sil independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, —[O—SiR Sim R Sin ] q —R Sio ,
wherein
q is an integer from 1 to 50,
R Sim , R Sin , R Sio independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, —[O—SiR Sip R Siq ] r —R Sir ,
wherein
r is an integer from 1 to 50,
R Sip , R Siq , R Sir are independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, O—Si(CH 3 ) 3 ,
C 1-30 -alkyl, C 2-30 -alkenyl and C 2-30 -alkynyl can be substituted with one to ten substituents selected from the group consisting of halogen and CN,
R 2 is at each occurrence selected from the group consisting of hydrogen, C 1-30 -alkyl and halogen,
wherein
C 1-30 -alkyl can be substituted with one to ten substituents independently selected from the group consisting of C 5-8 -cycloalkyl, C 6-14 -aryl, 5 to 14 membered heteroaryl, OR e , OC(O)—R e , C(O)—OR e , C(O)—R e , NR e R f , NR e —C(O)R f , C(O)—NR e R f , N[C(O)R e ][C(O)R f ], SR e , halogen, CN, SiR Sis R Sit R Siu and NO 2 ; and at least two CH 2 -groups, but not adjacent CH 2 -groups, of C 1-30 -alkyl can be replaced by O or S,
wherein
R Sis , R Sit R Siu are independently from each other selected from the group consisting of H, C 1-20 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-6 -cycloalkyl, phenyl and O—Si(CH 3 ) 3 ,
R e and R f are independently selected from the group consisting of H, C 2-20 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, and 5 to 14 membered heteroaryl,
wherein
C 1-20 -alkyl, C 2-20 -alkenyl and C 2-20 -alkynyl can be substituted with one to five substituents selected from the group consisting of C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR g , OC(O)—R g , C(O)—OR g , C(O)—R g , NR g R h , NR g —C(O)R h , C(O)—NR g R h , N[C(O)R g ][C(O)R h ], SR g , halogen, CN, and NO 2 ;
C 5-8 -cycloalkyl can be substituted with one to five substituents selected from the group consisting of C 1-10 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR g , OC(O)—R g , C(O)—OR g , C(O)—R g , NR g R h , NR g —C(O)R h , C(O)—NR g R h , N[C(O)R g ][C(O)R h ], SR g , halogen, CN, and NO 2 ;
C 6-14 -aryl and 5 to 14 membered heteroaryl can be substituted with one to five substituents independently selected from the group consisting of C 1-10 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR g , OC(O)—R g , C(O)—OR g , C(O)—R g , NR g R h , NR g —C(O)R h , C(O)—NR g R h , N[C(O)R g ][C(O)R h ], SR g , halogen, CN, and NO 2 ;
wherein
R g and R h are independently selected from the group consisting of H, C 1-10 -alkyl, C 2-10 -alkenyl and C 2-10 -alkynyl,
wherein
C 1-10 -alkyl, C 2-10 -alkenyl and C 2-10 -alkynyl can be substituted with one to five substituents selected from the group consisting of halogen, CN and NO 2 .
3. The polymer of claim 1 , wherein
R 1 is at each occurrence selected from the group consisting of C 1-100 -alkyl, C 2-100 -alkenyl and C 2-100 -alkynyl,
wherein
C 1-100 -alkyl, C 2-100 -alkenyl and C 2-100 -alkynyl can be substituted with one to forty substituents independently selected from the group consisting of C 5-8 -cycloalkyl, C 6-14 -aryl, 5 to 14 membered heteroaryl, OR a , OC(O)—R a , C(O)—OR a , C(O)—R a , NR a —C(O)R b , C(O)—NR a R b , SR a , Si(R Sia )(R Sib )(R Sic ), —O—Si(R Sia )(R Sib )(R Sic ), halogen, and CN; and at least two CH 2 -groups, but not adjacent CH 2 -groups, of C 1-100 -alkyl, C 2-100 -alkenyl and C 2-100 -alkynyl can be replaced by O or S,
wherein
R a and R b are independently selected from the group consisting of H, C 1-60 -alkyl, C 2-60 -alkenyl, C 2-60 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl and 5 to 14 membered heteroaryl,
R Sia , R Sib and R Sic independently selected from the group consisting of H, C 1-60 -alkyl, C 2-60 -alkenyl, C 2-60 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, —[O—SiR Sid R Sie ] o —R Sif ,
wherein
o is an integer from 1 to 50,
R Sid , R Sie and R Sif are independently selected from the group consisting of H, C 1-60 -alkyl, C 2-60 -alkenyl, C 2-60 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, —[O—SiR Sig R Sih ] p —R Sii ,
wherein
p is an integer from 1 to 50,
R Sig R Sih , R Sii are independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, O—Si(CH 3 ) 3 ,
C 1-60 -alkyl, C 2-60 -alkenyl and C 2-60 -alkynyl can be substituted with one to twenty substituents selected from the group consisting of C 5-6 -cycloalkyl, C 6-10 -aryl, OR c , OC(O)—R c , C(O)—OR c , C(O)—R c , NR c —C(O)R d , C(O)NR c R d , SR c , Si(R Sij )(R Sik )(R Sil ), —O—Si(R Sij )(R Sik )(R Sil ), halogen, and CN; and at least two CH 2 -groups, but not adjacent CH 2 -groups, of C 1-60 -alkyl, C 2-60 -alkenyl and C 2-60 -alkynyl can be replaced by O or S,
C 5-8 -cycloalkyl can be substituted with one to five substituents selected from the group consisting of C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, OR c , OC(O)—R c , C(O)—OR c , C(O)—R c , NR c —C(O)R d , C(O)—NR c R d , SR c , Si(R Sij )(R Sik )(R Sil ), —O—Si(R Sij )(R Sik )(R Sil ), halogen, and CN; and one or two CH 2 -groups, but not adjacent CH 2 -groups, of C 5-8 -cycloalkyl can be replaced by O, S, OC(O), CO, NR c or NR c —CO,
C 6-14 -aryl and 5 to 14 membered heteroaryl can be substituted with one to five substituents independently selected from the group consisting of C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, OR c , OC(O)—R c , C(O)—OR c , C(O)—R c , NR c —C(O)R d , C(O)—NR c R d , SR c , Si(R Sij )(R Sik )(R Sil ), —O—Si(R Sij )(R Sik )(R Sil ), halogen, and CN;
wherein
R c and R d are independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl and C 2-30 -alkynyl,
R Sij , R Sik and R Sil are independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, —[O—SiR Sim R Sin ] q —R Sio ,
wherein
q is an integer from 1 to 50,
R Sim , R Sin , R Sio independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, —[O—SiR Sip R Siq ] r —R Sir ,
wherein
r is an integer from 1 to 50,
R Sip , R Siq , R Sir are independently selected from the group consisting of H, C 1-30 -alkyl, C 2-30 -alkenyl, C 2-30 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, O—Si(CH 3 ) 3 ,
C 1-30 -alkyl, C 2-30 -alkenyl and C 2-30 -alkynyl can be substituted with one to ten substituents selected from the group consisting of halogen and CN,
R 2 is at each occurrence selected from the group consisting of hydrogen, C 1-30 -alkyl and halogen,
wherein
C 1-30 -alkyl can be substituted with one to ten substituents independently selected from the group consisting of C 5-8 -cycloalkyl, C 6-14 -aryl, 5 to 14 membered heteroaryl, OR e , OC(O)—R e , C(O)—OR e , C(O)—R e , NR e R f , NR e —C(O)R f , C(O)—NR e R f , N[C(O)R e ][C(O)R f ], SR e , halogen, CN, SiR Sis R Sil R Siu and NO 2 ; and at least two CH 2 -groups, but not adjacent CH 2 -groups, of C 1-30 -alkyl can be replaced by O or S,
wherein
R Sis , R Sit and R Siu are independently from each other selected from the group consisting of H, C 1-20 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-6 -cycloalkyl, phenyl and O—Si(CH 3 ) 3 ,
R e and R f are independently selected from the group consisting of H, C 1-20 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-8 -cycloalkyl, C 6-14 -aryl, and 5 to 14 membered heteroaryl,
wherein
C 1-20 -alkyl, C 2-20 -alkenyl and C 2-20 -alkynyl can be substituted with one to five substituents selected from the group consisting of C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR g , OC(O)—R g , C(O)—OR g , C(O)—R g , NR g R h , NR g —C(O)R h , C(O)—NR g R h , N[C(O)R g ][C(O)R h ], SR g , halogen, CN, and NO 2 ;
C 5-8 -cycloalkyl can be substituted with one to five substituents selected from the group consisting of C 1-10 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR g , OC(O)—R g , C(O)—OR g , C(O)—R g , NR g R h , NR g —C(O)R h , C(O)—NR g R h , N[C(O)R g ][C(O)R h ], SR g , halogen, CN, and NO 2 ;
C 6-14 -aryl and 5 to 14 membered heteroaryl can be substituted with one to five substituents independently selected from the group consisting of C 1-10 -alkyl, C 2-10 -alkenyl, C 2-10 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR g , OC(O)—R g , C(O)—OR g , C(O)—R g , NR g R h , NR g —C(O)R h , C(O)—NR g R h , N[C(O)R g ][C(O)R h ], SR g , halogen, CN, and NO 2 :
wherein
R g and R h are independently selected from the group consisting of H, C 1-10 -alkyl, C 2-10 -alkenyl and C 2-10 -alkynyl,
wherein
C 1-10 -alkyl, C 2-10 -alkenyl and C 2-10 -alkynyl can be substituted with one to five substituents selected from the group consisting of halogen, CN and NO 2 .
4. The polymer of claim 1 wherein
R 1 is at each occurrence selected from the group consisting of C 1-36 -alkyl, C 2-36 -alkenyl and C 2-36 -alkynyl,
wherein
C 1-36 -alkyl, C 2-36 -alkenyl and C 2-36 -alkynyl can be substituted with one to twenty substituents independently selected from the group consisting of C 5-6 -cycloalkyl, C 6-10 -aryl, 5 to 10 membered heteroaryl, OR a , SR a , Si(R Sia )(R Sib )(R Sic ), —O—Si(R Sia )(R Sib )(R Sic ), halogen, and CN; and at least two CH 2 -groups, but not adjacent CH 2 -groups, of C 1-36 -alkyl, C 2-36 -alkenyl and C 2-36 -alkynyl can be replaced by O or S,
wherein
R a is independently selected from the group consisting of H, C 1-20 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-6 -cycloalkyl and C 6-10 -aryl
R Sia , R Sib and R Sic are independently selected from the group consisting of H, C 1-20 -M-alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, —[O—SiR Sid R Sie ] o —R Sif
wherein
o is an integer from 1 to 50,
R Sid , R Sic , R Sif independently selected from the group consisting of H, C 1-30 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, —[O—SiR Sig R Sih ] p —R Sii ,
wherein
p is an integer from 1 to 50,
R Sig R Sih , R Sii independently selected from the group consisting of H, C 1-20 -alkyl, C 2-20 -alkenyl, C 2-20 -alkynyl, C 5-6 -cycloalkyl, C 6-10 -aryl, O—Si(CH 3 ) 3 ,
C 1-20 -alkyl, C 2-20 -alkenyl and C 2-20 -alkynyl can be substituted with one to ten substituents selected from the group consisting of halogen and CN,
R 2 is at each occurrence selected from the group consisting of unsubstituted hydrogen, C 1-30 -alkyl and halogen.
5. The polymer of claim 1 , wherein
R 1 is at each occurrence unsubstituted C 1-36 -alkyl, and
R 2 is at each occurrence hydrogen.
6. The polymer of claim 1 , wherein
n is 0, 1 or 2, and
m is 0, 1 or 2,
with the proviso that at least one of n and m is not 0.
7. A process for preparing the polymer of claim 1 ,
wherein the formula (1) is formula (1-I)
the process comprising:
reacting a compound of formula (2)
wherein Y is at each occurrence I, Br, Cl or O—S(O) 2 CF 3 ,
with a compound of formula (3)
wherein
Z a and Z b are independently selected from the group consisting of B(OZ 1 )(OZ 2 ), SnZ 1 Z 2 Z 3 ,
wherein Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 are independently from each other and at each occurrence H or C 1-4 -alkyl.
8. An electronic device, comprising:
a polymer of claim 1 .
9. The electronic device of claim 8 , wherein the electronic device is an organic field effect transistor.