Semiconducting polymer

Abstract

Compounds of formula (I) and polymers comprising at least a structure of formula (II), wherein T.sup.1 or T.sup.2 are independently of each other a group of Formula (III), Formula (iv) Q.sup.a, Q.sup.b, Q.sup.c, Q.sup.d, Q.sup.e or Q.sup.f are independently of each other O, S or NR.sup.1. ##STR00001## ##STR00002##

Claims

1. A polymer, consisting of unit having a structure of formula (II) ##STR00073## wherein Q.sup.a, Q.sup.b, Q.sup.c and Q.sup.d are independently O, S or an NR.sup.1 group, Ar and Ar are independently selected from the group consisting of ##STR00074## ##STR00075## each Y, Y, Y and Y* is independently O, S, an NR.sup.1a group, Se, or Te, and each R.sup.W is independently H, a C.sub.1-30-alkyl group, a C.sub.1-30-alkoxy group, or a moiety ##STR00076## R.sup.s1, R.sup.s2 and R.sup.s3 are independently H, a C.sub.1-20-alkyl group, a C.sub.2-20-alkenyl group, or a phenyl group, Ar or Ar is bound via the single bonds and to the moieties ##STR00077## Q is Q.sup.a, Q.sup.b, Q.sup.c or Q.sup.d, Ar and/or Ar optionally comprise a substituent R.sup.2, each R.sup.1 and R.sup.1a is independently selected from the group consisting of H, a C.sub.1-100-alkyl group, a C.sub.2-100-alkenyl group, a C.sub.2-100-alkynyl group, a C.sub.5-12-cycloalkyl group, a C.sub.6-18-aryl group, a 5 to 20 membered heteroaryl group, a C(O)C.sub.1-100-alkyl group, a C(O)C.sub.5-12-cycloalkyl group and a C(O)OC.sub.1-100-alkyl group, the C.sub.1-100-alkyl group, the C.sub.2-100-alkenyl group and the C.sub.2-100-alkynyl group optionally comprise one to forty substituents independently selected from the group consisting of a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, a 5 to 14 membered heteroaryl group, an OR.sup.a group, an OC(O)R.sup.a group, a C(O)OR.sup.a group, a C(O)R.sup.a group, an NR.sup.aR.sup.b group, an NR.sup.aC(O)R.sup.b group, a C(O)NR.sup.aR.sup.b group, an N[C(O)R.sup.a][C(O)R.sup.b] group, an SR.sup.a group, an Si(R.sup.Sia)(R.sup.Sib)(R.sup.Sic) group, an OSi(R.sup.Sia)(R.sup.Sib)(R.sup.Sic) group, a halogen, CN, and NO.sub.2, at least two CH.sub.2-groups, but not adjacent CH.sub.2-groups, of the C.sub.1-100-alkyl group, the C.sub.2-100-alkenyl group and/or the C.sub.2-100-alkynyl group can be replaced by O or S, the C.sub.5-12-cycloalkyl group optionally comprises one to six substituents independently selected from the group consisting of a C.sub.1-60-alkyl group, a C.sub.2-60-alkenyl group, a C.sub.2-60-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, a 5 to 14 membered heteroaryl group, an OR.sup.a group, an OC(O)R.sup.a group, a C(O)OR.sup.a group, a C(O)R.sup.a group, an NR.sup.aR.sup.b group, an NR.sup.aC(O)R.sup.b group, a C(O)NR.sup.aR.sup.b group, an N[C(O)R.sup.a][C(O)R.sup.b] group, an SR.sup.a group, an Si(R.sup.Sia)(R.sup.Sib)(R.sup.Sic) group, an OSi(R.sup.Sia)(R.sup.Sib)(R.sup.Sic) group, a halogen, CN, and NO.sub.2, one or two CH.sub.2-groups, but not adjacent CH.sub.2-groups, of the C.sub.5-12-cycloalkyl group can be replaced by O, S, OC(O), CO, an NR.sup.a group or an NR.sup.aCO group, the C.sub.6-18-aryl group and the 5 to 20 membered heteroaryl group optionally comprise one to six substituents independently selected from the group consisting of a C.sub.1-60-alkyl group, a C.sub.2-60-alkenyl group, a C.sub.2-60-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, a 5 to 14 membered heteroaryl group, an OR.sup.a group, an OC(O)R.sup.a group, a C(O)OR.sup.a group, a C(O)R.sup.a group, an NR.sup.aR.sup.b group, an NR.sup.aC(O)R.sup.b group, a C(O)NR.sup.aR.sup.b group, an N[C(O)R.sup.a][C(O)R.sup.b] group, an SR.sup.a group, an Si(R.sup.Sia)(R.sup.Sib)(R.sup.Sic) group, an OSi(R.sup.Sia)(R.sup.Sib)(R.sup.Sic) group, a halogen, CN, and NO.sub.2, R.sup.a and R.sup.b are independently selected from the group consisting of H, a C.sub.1-60-alkyl group, a C.sub.2-60-alkenyl group, a C.sub.2-60-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group and a 5 to 14 membered heteroaryl group, R.sup.Sia, R.sup.Sib and R.sup.Sic are independently selected from the group consisting of H, a C.sub.1-60-alkyl group, a C.sub.2-60-alkenyl group, a C.sub.2-60-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, a 5 to 14 membered heteroaryl group, an OC.sub.1-60-alkyl group, an OC.sub.2-60-alkenyl group, an OC.sub.2-60-alkynyl group, an OC.sub.5-8-cycloalkyl group, an OC.sub.6-14-aryl group, an O-5 to 14 membered heteroaryl group, an [OSiR.sup.SidR.sup.Sie].sub.oR.sup.Sif group, an NR.sup.5R.sup.6 group, a halogen and an OC(O)R.sup.5 group, o is an integer from 1 to 50, R.sup.Sid, R.sup.Sie, R.sup.Sif are independently selected from the group consisting of H, a C.sub.1-60-alkyl group, a C.sub.2-60-alkenyl group, a C.sub.2-60-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, a 5 to 14 membered heteroaryl group, an OC.sub.1-60-alkyl group, an OC.sub.2-60-alkenyl group, an OC.sub.2-60-alkynyl group, an OC.sub.5-8-cycloalkyl group, an OC.sub.6-14-aryl group, an O-5 to 14 membered heteroaryl group, an [OSiR.sup.SigR.sup.Sih].sub.pR.sup.Sii group, an NR.sup.50R.sup.60 group, a halogen and an OC(O)R.sup.50 group, p is an integer from 1 to 50, R.sup.Sig R.sup.Sih, R.sup.Sii are independently selected from the group consisting of H, a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group, a C.sub.2-30-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OC.sub.1-30-alkyl group, an OC.sub.2-30-alkenyl group, an OC.sub.2-30-alkynyl group, an OC.sub.5-6-cycloalkyl group, an OC.sub.6-10-aryl group, an O-5 to 10 membered heteroaryl group, an OSi(CH.sub.3).sub.3 group, an NR.sup.500R.sup.600 group, a halogen and an OC(O)R.sup.500 group, R.sup.5, R.sup.6, R.sup.50, R.sup.60, R.sup.500 and R.sup.600 are independently selected from the group consisting of H, a C.sub.1-60-alkyl group, a C.sub.2-60-alkenyl group, a C.sub.2-60-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, and a 5 to 14 membered heteroaryl group, the C.sub.1-60-alkyl group, the C.sub.2-60-alkenyl group and the C.sub.2-60-alkynyl group optionally comprise one to twenty substituents selected from the group consisting of a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, an OR.sup.c group, an OC(O)R.sup.c group, a C(O)OR.sup.c group, a C(O)R.sup.c group, an NR.sup.cR.sup.d group, an NR.sup.cC(O)R.sup.d group, a C(O)NR.sup.cR.sup.d group, an N[C(O)R.sup.c][C(O)R.sup.d] group, an SR.sup.c group, an Si(R.sup.Sij)(R.sup.Sik)(R.sup.Sil) group, an OSi(R.sup.Sij)(R.sup.Sik)(R.sup.Sil) group, a halogen, CN, and NO.sub.2, at least two CH.sub.2-groups, but not adjacent CH.sub.2-groups, of the C.sub.1-60-alkyl group, the C.sub.2-60-alkenyl group and/or the C.sub.2-60-alkynyl group can be replaced by O or S, the C.sub.5-8-cycloalkyl group optionally comprises one to five substituents selected from the group consisting of a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group, a C.sub.2-30-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, an OR group, an OC(O)R.sup.c group, a C(O)OR.sup.c group, an C(O)R.sup.c group, an NR.sup.cR.sup.d group, an NR.sup.cC(O)R.sup.d group, a C(O)NR.sup.cR.sup.d group, an N[C(O)R.sup.c][C(O)R.sup.d] group, an SR.sup.c group, an Si(R.sup.Sij)(R.sup.Sik)(R.sup.Sil) group, an OSi(R.sup.Sij)(R.sup.Sik)(R.sup.Sil) group, a halogen, CN, and NO.sub.2, one or two CH.sub.2-groups, but not adjacent CH.sub.2-groups, of the C.sub.5-8-cycloalkyl group can be replaced by O, S, OC(O), CO, an NR group or an NR.sup.cCO group, the C.sub.6-14-aryl group and the 5 to 14 membered heteroaryl group optionally comprise one to five substituents independently selected from the group consisting of a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group, a C.sub.2-30-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, an OR group, an OC(O)R.sup.c group, a C(O)OR.sup.c group, a C(O)R.sup.c group, an NR.sup.cR.sup.d group, an NR.sup.cC(O)R.sup.d group, a C(O)NR.sup.cR.sup.d group, an N[C(O)R.sup.c][C(O)R.sup.d] group, an SR.sup.c group, an Si(R.sup.Sij)(R.sup.Sik)(R.sup.Sil) group, an OSi(R.sup.Sij)(R.sup.Sik)(R.sup.Sil) group, a halogen, CN and NO.sub.2, R.sup.c and R.sup.d are independently selected from the group consisting of H, a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group and a C.sub.2-30-alkynyl group, R.sup.Sij, R.sup.Sik and R.sup.Sil are independently selected from the group consisting of H, a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group, a C.sub.2-30-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OC.sub.1-30-alkyl group, an OC.sub.2-30-alkenyl group, an OC.sub.2-30-alkynyl group, an OC.sub.5-6-cycloalkyl group, an OC.sub.6-10-aryl group, an O-5 to 10 membered heteroaryl group, an [OSiR.sup.SimR.sup.Sin].sub.qR.sup.Sio group, an NR.sup.7R.sup.8 group, a halogen, and an OC(O)R.sup.7 group, q is an integer from 1 to 50, R.sup.Sim, R.sup.Sin, R.sup.Sio are independently selected from the group consisting of H, a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group, a C.sub.2-30-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OC.sub.1-30-alkyl group, an OC.sub.2-30-alkenyl group, an OC.sub.2-30-alkynyl group, an OC.sub.5-6-cycloalkyl group, an OC.sub.6-10-aryl group, an O-5 to 10 membered heteroaryl group, an [OSiR.sup.SipR.sup.Siq].sub.rR.sup.Sir group, an NR.sup.70R.sup.80 group, a halogen, and an OC(O)R.sup.70 group, r is an integer from 1 to 50, R.sup.Sip, R.sup.Siq, R.sup.Sir are independently selected from the group consisting of H, a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group, a C.sub.2-30-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OC.sub.1-30-alkyl group, an OC.sub.2-30-alkenyl group, an OC.sub.2-30-alkynyl group, an OC.sub.5-6-cycloalkyl group, an OC.sub.6-10-aryl group, an O-5 to 10 membered heteroaryl group, an OSi(CH.sub.3).sub.3 group, an NR.sup.700R.sup.800 group, a halogen and an OC(O)R.sup.700 group, R.sup.7, R.sup.8, R.sup.70, R.sup.80, R.sup.700 and R.sup.800 are independently selected from the group consisting of H, a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group, a C.sub.2-30-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, and a 5 to 10 membered heteroaryl group, the C.sub.1-30-alkyl group, the C.sub.2-30-alkenyl group and the C.sub.2-30-alkynyl group optionally comprise one to ten substituents selected from the group consisting of a halogen, CN and NO.sub.2, each R.sup.2 is selected from the group consisting of a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group, a C.sub.2-30-alkynyl group, a C.sub.5-12-cycloalkyl group, a C.sub.6-18-aryl group, a 5 to 20 membered heteroaryl group, an OR.sup.21 group, an OC(O)R.sup.21 group, a C(O)OR.sup.21 group, a C(O)R.sup.21 group, an NR.sup.21R.sup.22 group, an NR.sup.21C(O)R.sup.22 group, a C(O)NR.sup.21R.sup.22 group, an N[C(O)R.sup.21][C(O)R.sup.22] group, an SR.sup.21 group, a halogen, CN, an SiR.sup.SisR.sup.SitR.sup.Sin group and OH, R.sup.21 and R.sup.22 and are independently selected from the group consisting of H, a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group, a C.sub.2-30-alkynyl group, a C.sub.5-12-cycloalkyl group, a C.sub.6-18-aryl group and a 5 to 20 membered heteroaryl group, the C.sub.1-30-alkyl group, the C.sub.2-30-alkenyl group and the C.sub.2-30-alkynyl group optionally comprise one to ten substituents independently selected from the group consisting of a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, a 5 to 14 membered heteroaryl group, an OR.sup.e group, an OC(O)R.sup.e group, a C(O)OR.sup.e group, a C(O)R.sup.e group, an NR.sup.eR.sup.f group, an NR.sup.eC(O)R.sup.f group, a C(O)NR.sup.eR.sup.f group, an N[C(O)R.sup.e][C(O)R.sup.f] group, an SR.sup.e group, a halogen, CN, an SiR.sup.SisR.sup.SitR.sup.Siu group and NO.sub.2, at least two CH.sub.2-groups, but not adjacent CH.sub.2-groups, of the C.sub.1-30-alkyl group, the C.sub.2-30-alkenyl group and/or the C.sub.2-30-alkynyl group can be replaced by O or S, the C.sub.5-12-cycloalkyl optionally comprises one to six substituents independently selected from the group consisting of a C.sub.1-20-alkyl group, a C.sub.2-20-alkenyl group, a C.sub.2-20-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, a 5 to 14 membered heteroaryl group, an OR.sup.e group, an OC(O)R.sup.e group, a C(O)OR.sup.e group, a C(O)R.sup.e group, an NR.sup.eR.sup.f group, an NR.sup.eC(O)R.sup.f group, a C(O)NR.sup.eR.sup.f group, an N[C(O)R.sup.e][C(O)R.sup.f] group, an SR.sup.e group, a halogen, CN, an SiR.sup.SisR.sup.SitR.sup.Siu group and NO.sub.2, one or two CH.sub.2-groups, but not adjacent CH.sub.2-groups, of the C.sub.5-12-cycloalkyl group can be replaced by O, S, OC(O), CO, an NR.sup.e group or an NR.sup.eCO group, and the C.sub.6-18-aryl group and the 5 to 20 membered heteroaryl group optionally comprise one to six substituents independently selected from the group consisting of a C.sub.1-20-alkyl group, a C.sub.2-20-alkenyl group, a C.sub.2-20-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, a 5 to 14 membered heteroaryl group, an OR.sup.e group, an OC(O)R.sup.e group, a C(O)OR.sup.e group, a C(O)R.sup.e group, an NR.sup.eR.sup.f group, an NR.sup.eC(O)R.sup.f group, a C(O)NR.sup.eR.sup.f group, an N[C(O)R.sup.e][C(O)R.sup.f] group, an SR.sup.e group, a halogen, CN, an SiR.sup.SisR.sup.SitR.sup.Siu group and NO.sub.2, R.sup.Sis, R.sup.Sit and R.sup.Siu are independently selected from the group consisting of H, a C.sub.1-20-alkyl group, a C.sub.2-20-alkenyl group, a C.sub.2-20-alkynyl group, a C.sub.5-6-cycloalkyl group, a phenyl group and an OSi(CH.sub.3).sub.3 group, R.sup.e and R.sup.f are independently selected from the group consisting of H, a C.sub.1-20-alkyl group, a C.sub.2-20-alkenyl group, a C.sub.2-20-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, and a 5 to 14 membered heteroaryl group, the C.sub.1-20-alkyl group, the C.sub.2-20-alkenyl group and the C.sub.2-20-alkynyl group optionally comprise one to five substituents selected from the group consisting of a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OR.sup.g group, an OC(O)R.sup.g group, a C(O)OR.sup.g group, a C(O)R.sup.g group, an NR.sup.gR.sup.h group, an NR.sup.gC(O)R.sup.h group, a C(O)NR.sup.gR.sup.h group, an N[C(O)R.sup.g][C(O)R.sup.h] group, an SR.sup.g group, a halogen, CN, and NO.sub.2, the C.sub.5-8-cycloalkyl group optionally comprises one to five substituents selected from the group consisting of a C.sub.1-10-alkyl group, a C.sub.2-10-alkenyl group, a C.sub.2-10-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OR.sup.g group, an OC(O)R.sup.g group, a C(O)OR group, a C(O)R group, an NR.sup.gR.sup.h group, an NR.sup.gC(O)R.sup.h group, a C(O)NR.sup.gR.sup.h group, an N[C(O)R.sup.g][C(O)R.sup.h] group, an SR.sup.g group, a halogen, CN, and NO.sub.2, the C.sub.6-14-aryl group and the 5 to 14 membered heteroaryl group optionally comprise one to five substituents independently selected from the group consisting of a C.sub.1-10-alkyl group, a C.sub.2-10-alkenyl group, a C.sub.2-10-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OR.sup.g group, an OC(O)R group, a C(O)OR.sup.g group, a C(O)R group, an NR.sup.gR.sup.h group, an NR.sup.gC(O)R.sup.h group, a C(O)NR.sup.gR.sup.h group, an N[C(O)R.sup.g][C(O)R.sup.h] group, an SR.sup.g group, a halogen, CN, and NO.sub.2, R.sup.g and R.sup.h are independently selected from the group consisting of H, a C.sub.1-10-alkyl group, a C.sub.2-10-alkenyl group and a C.sub.2-10-alkynyl group, the C.sub.1-10-alkyl group, the C.sub.2-10-alkenyl group and the C.sub.2-10-alkynyl group optionally comprise one to five substituents selected from the group consisting of a halogen, CN and NO.sub.2, each R.sup.100 and R.sup.101 is independently selected from the group consisting of H, a C.sub.1-20-alkyl group, a C.sub.2-20-alkenyl group, a C.sub.2-20-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, and a 5 to 14 membered heteroaryl group; or wherein R.sup.100 and R.sup.101, if attached to a same atom, together with the same atom, form a 5 to 12 membered ring system, the C.sub.1-20-alkyl group, the C.sub.2-20-alkenyl group and the C.sub.2-20-alkynyl group optionally comprise one to five substituents selected from the group consisting of a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OR.sup.q group, an OC(O)R.sup.q group, a C(O)OR.sup.q group, a C(O)R.sup.q group, an NR.sup.qR.sup.r group, an NR.sup.qC(O)R.sup.r group, a C(O)NR.sup.gR.sup.r group, an N[C(O)R.sup.q][C(O)R.sup.r] group, an SR.sup.q group, a halogen, CN, and NO.sub.2, the C.sub.5-8-cycloalkyl group optionally comprises one to five substituents selected from the group consisting of a C.sub.1-10-alkyl group, a C.sub.2-10-alkenyl group, a C.sub.2-10-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OR.sup.q group, an OC(O)R.sup.q group, a C(O)OR.sup.q group, a C(O)R.sup.q group, an NR.sup.qR.sup.r group, an NR.sup.qC(O)R.sup.r group, a C(O)NR.sup.qR.sup.r group, an N[C(O)R.sup.q][C(O)R.sup.r] group, an SR.sup.q group, a halogen, CN, and NO.sub.2, the C.sub.6-14-aryl group and the 5 to 14 membered heteroaryl group optionally comprise one to five substituents independently selected from the group consisting of a C.sub.1-10-alkyl group, a C.sub.2-10-alkenyl group, a C.sub.2-10-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OR.sup.q group, an OC(O)R.sup.g group, a C(O)OR.sup.g group, a C(O)R.sup.g group, an NR.sup.qR.sup.r group, an NR.sup.qC(O)R.sup.r group, a C(O)NR.sup.qR.sup.r group, an N[C(O)R.sup.q][C(O)R.sup.r] group, a SR.sup.q group, a halogen, CN, and NO.sub.2, the 5 to 12 membered ring system optionally comprises one to five substituents selected from the group consisting of a C.sub.1-10-alkyl group, a C.sub.2-10-alkenyl group, a C.sub.2-10-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OR.sup.q group, an OC(O)R.sup.g group, a C(O)OR.sup.g group, a C(O)R.sup.g group, an NR.sup.qR.sup.r group, an NR.sup.qC(O)R.sup.r group, a C(O)NR.sup.qR.sup.r group, an N[C(O)R.sup.q][C(O)R.sup.r] group, an SR.sup.q group, a halogen, CN, and NO.sub.2, R.sup.q and R.sup.r are independently selected from the group consisting of H, a C.sub.1-10alkyl group, a C.sub.2-10-alkenyl group and a C.sub.2-10-alkynyl group, the C.sub.1-10-alkyl group, the C.sub.2-10-alkenyl group and the C.sub.2-10-alkynyl group optionally comprise one to five substituents selected from the group consisting of a halogen, CN and NO.sub.2, and n is in a range from 3 to 1000.

2. The polymer of claim 1, wherein Ar and Ar are independently selected from the group consisting of ##STR00078## ##STR00079##

3. The polymer of claim 1, wherein Ar and Ar are independently selected from the group consisting of ##STR00080##

4. The polymer of claim 1, consisting of units having a structure of formula 1, 2 or 3 ##STR00081## wherein R.sup.1b, R.sup.1c and R.sup.1d are independently defined as R.sup.1a.

5. A polymer consisting of units having a a structure of formula II ##STR00082## Q.sup.a and Q.sup.b are independently O, S or an NR.sup.1 group, Ar is selected from the group consisting of: ##STR00083## ##STR00084## each Y, Y, Y and Y* is independently O, S, and NR.sup.1a group, Se, or Te, and each R.sup.W is independently H, a C.sub.1-20-alkyl group, a C.sub.1-30-alkoxy group, or a moiety: ##STR00085## R.sup.a1, R.sup.a2 and R.sup.a3 are independently H, a C.sub.1-20-alkyl group, a C.sub.2-20-alkenyl group or a phenyl group, Ar or Ar is bound viathe single bonds and to the moieties: ##STR00086## Q is Q.sup.a, Q.sup.b, Q.sup.c, or Q.sup.d, Ar and/or Ar optionally comprise a substituent R.sup.2, each R.sup.1 and R.sup.1a is independently selected from the group consisting of H, a C.sub.1-100-alkyl group, a C.sub.2-100-alkenyl group, a C.sub.2-100-alkynyl group, a C.sub.5-12-cycloalkyl group, a C.sub.6-18-aryl group, a 5 to 20 membered heteroaryl group, a C(O)C.sub.1-100-alkyl group, a C(O)C.sub.5-12-cycloalkyl group and a C(O)OC.sub.1-100-alkyl group, the C.sub.1-100-alkyl group, the C.sub.2-100-alkenyl group and the C.sub.2-100-alkynyl group optionally comprise one to forty substituents independently selected from the group consisting of a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, a 5 to 14 membered heteroaryl group, an OR.sup.a group, an OC(O)R.sup.a group, a C(O)OR.sup.a group, a C(O)R.sup.a group, an NR.sup.aR.sup.b group, an NR.sup.aC(O)R.sup.b group, a C(O)NR.sup.aR.sup.b group, an N[C(O)R.sup.a][C(O)R.sup.b] group, an SR.sup.a group, an Si(R.sup.Sia)(R.sup.Sib)(R.sup.Sic) group, an OSi(R.sup.Sia)(R.sup.Sib)(R.sup.Sic) group, a halogen, CN, and NO.sub.2, at least two CH.sub.2-groups, but not adjacent CH.sub.2-groups, of the C.sub.1-100-alkyl group, the C.sub.2-100-alkenyl group and/or the C.sub.2-100-alkynyl group can be replaced by O or S, the C.sub.5-12-cycloalkyl group optionally comprises one to six substituents independently selected from the group consisting of a C.sub.1-60-alkyl group, a C.sub.2-60-alkenyl group, a C.sub.2-60-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, a 5 to 14 membered heteroaryl group, an OR.sup.a group, an OC(O)R.sup.a group, a C(O)OR.sup.a group, a C(O)R.sup.a group, an NR.sup.aR.sup.b group, an NR.sup.aC(O)R.sup.b group, a C(O)NR.sup.aR.sup.b group, an N[C(O)R.sup.a][C(O)R.sup.b] group, an SR.sup.a group, an Si(R.sup.Sia)(R.sup.Sib)(R.sup.Sic) group, an OSi(R.sup.Sia)(R.sup.Sib)(R.sup.Sic) group, a halogen, CN, and NO.sub.2, one or two CH.sub.2-groups, but not adjacent CH.sub.2-groups, of the C.sub.5-12-cycloalkyl group can be replaced by O, S, OC(O), CO, an NR.sup.a group or an NR.sup.aCO group, the C.sub.6-18-aryl group and the 5 to 20 membered heteroaryl group optionally comprise one to six substituents independently selected from the group consisting of a C.sub.1-60-alkyl group, a C.sub.2-60-alkenyl group, a C.sub.2-60-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, a 5 to 14 membered heteroaryl group, an OR.sup.a group, an OC(O)R.sup.a group, a C(O)OR.sup.a group, a C(O)R.sup.a group, an NR.sup.aR.sup.b group, an NR.sup.aC(O)R.sup.b group, a C(O)NR.sup.aR.sup.b group, an N[C(O)R.sup.a][C(O)R.sup.b] group, an SR.sup.a group, an Si(R.sup.Sia)(R.sup.Sib)(R.sup.Sic) group, an OSi(R.sup.Sia)(R.sup.Sib)(R.sup.Sic) group, a halogen, CN, and NO.sub.2, R.sup.a and R.sup.b are independently selected from the group consisting of H, a C.sub.1-60-alkyl group, a C.sub.2-60-alkenyl group, a C.sub.2-60-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group and a 5 to 14 membered heteroaryl group, R.sup.Sia, R.sup.Sib and R.sup.Sic are independently selected from the group consisting of H, a C.sub.1-60-alkyl group, a C.sub.2-60-alkenyl group, a C.sub.2-60-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, a 5 to 14 membered heteroaryl group, an OC.sub.1-60-alkyl group, an OC.sub.2-60-alkenyl group, an OC.sub.2-60-alkynyl group, an OC.sub.5-8-cycloalkyl group, an OC.sub.6-14-aryl group, an O-5 to 14 membered heteroaryl group, an [OSiR.sup.SidR.sup.Sie].sub.oR.sup.Sif group, an NR.sup.5R.sup.6 group, a halogen and an OC(O)R.sup.5 group, o is an integer from 1 to 50, R.sup.Sid, R.sup.Sie, R.sup.Sif are independently selected from the group consisting of H, a C.sub.1-60-alkyl group, a C.sub.2-60-alkenyl group, a C.sub.2-60-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, a 5 to 14 membered heteroaryl group, an OC.sub.1-60-alkyl group, an OC.sub.2-60-alkenyl group, an OC.sub.2-60-alkynyl group, an OC.sub.5-8-cycloalkyl group, an OC.sub.6-14-aryl group, an O-5 to 14 membered heteroaryl group, an [OSiR.sup.SigR.sup.Sih].sub.pR.sup.Sii group, an NR.sup.50R.sup.60 group, a halogen and an OC(O)R.sup.50 group, p is an integer from 1 to 50, R.sup.Sig R.sup.Sih, R.sup.Sii are independently selected from the group consisting of H, a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group, a C.sub.2-30-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OC.sub.1-30-alkyl group, an OC.sub.2-30-alkenyl group, an OC.sub.2-30-alkynyl group, an OC.sub.5-6-cycloalkyl group, an OC.sub.6-10-aryl group, an O-5 to 10 membered heteroaryl group, an OSi(CH.sub.3).sub.3 group, an NR.sup.500R.sup.600 group, a halogen and an OC(O)R.sup.500 group, R.sup.5, R.sup.6, R.sup.50, R.sup.60, R.sup.500 and R.sup.600 are independently selected from the group consisting of H, a C.sub.1-60-alkyl group, a C.sub.2-60-alkenyl group, a C.sub.2-60-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, and a 5 to 14 membered heteroaryl group, the C.sub.1-60-alkyl group, the C.sub.2-60-alkenyl group and the C.sub.2-60-alkynyl group optionally comprise one to twenty substituents selected from the group consisting of a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, an OR.sup.c group, an OC(O)R.sup.c group, a C(O)OR.sup.c group, a C(O)R.sup.c group, an NR.sup.cR.sup.d group, an NR.sup.cC(O)R.sup.d group, a C(O)NR.sup.cR.sup.d group, an N[C(O)R.sup.c][C(O)R.sup.d] group, an SR.sup.c group, an Si(R.sup.Sij)(R.sup.Sik)(R.sup.Sil) group, an OSi(R.sup.Sij)(R.sup.Sik)(R.sup.Sil) group, a halogen, CN, and NO.sub.2, at least two CH.sub.2-groups, but not adjacent CH.sub.2-groups, of the C.sub.1-60-alkyl group, the C.sub.2-60-alkenyl group and/or the C.sub.2-60-alkynyl group can be replaced by O or S, the C.sub.5-8-cycloalkyl group optionally comprises one to five substituents selected from the group consisting of a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group, a C.sub.2-30-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, an OR group, an OC(O)R.sup.c group, a C(O)OR.sup.c group, an C(O)R.sup.c group, an NR.sup.cR.sup.d group, an NR.sup.cC(O)R.sup.d group, a C(O)NR.sup.cR.sup.d group, an N[C(O)R.sup.c][C(O)R.sup.d] group, an SR.sup.c group, an Si(R.sup.Sij)(R.sup.Sik)(R.sup.Sil) group, an OSi(R.sup.Sij)(R.sup.Sik)(R.sup.Sil) group, a halogen, CN, and NO.sub.2, one or two CH.sub.2-groups, but not adjacent CH.sub.2-groups, of the C.sub.5-8-cycloalkyl group can be replaced by O, S, OC(O), CO, an NR group or an NR.sup.cCO group, the C.sub.6-14-aryl group and the 5 to 14 membered heteroaryl group optionally comprise one to five substituents independently selected from the group consisting of a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group, a C.sub.2-30-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, an OR group, an OC(O)R.sup.c group, a C(O)OR.sup.c group, a C(O)R.sup.c group, an NR.sup.cR.sup.d group, an NR.sup.cC(O)R.sup.d group, a C(O)NR.sup.cR.sup.d group, an N[C(O)R.sup.c][C(O)R.sup.d] group, an SR.sup.c group, an Si(R.sup.Sij)(R.sup.Sik)(R.sup.Sil) group, an OSi(R.sup.Sij)(R.sup.Sik)(R.sup.Sil) group, a halogen, CN and NO.sub.2, R.sup.c and R.sup.d are independently selected from the group consisting of H, a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group and a C.sub.2-30-alkynyl group, R.sup.Sij, R.sup.Sik and R.sup.Sil are independently selected from the group consisting of H, a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group, a C.sub.2-30-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OC.sub.1-30-alkyl group, an OC.sub.2-30-alkenyl group, an OC.sub.2-30-alkynyl group, an OC.sub.5-6-cycloalkyl group, an OC.sub.6-10-aryl group, an O-5 to 10 membered heteroaryl group, an [OSiR.sup.SimR.sup.Sin].sub.qR.sup.Sio group, an NR.sup.7R.sup.8 group, a halogen, and an OC(O)R.sup.7 group, q is an integer from 1 to 50, R.sup.Sim, R.sup.Sin, R.sup.Sio are independently selected from the group consisting of H, a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group, a C.sub.2-30-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OC.sub.1-30-alkyl group, an OC.sub.2-30-alkenyl group, an OC.sub.2-30-alkynyl group, an OC.sub.5-6-cycloalkyl group, an OC.sub.6-10-aryl group, an O-5 to 10 membered heteroaryl group, an [OSiR.sup.SipR.sup.Siq].sub.rR.sup.Sir group, an NR.sup.70R.sup.80 group, a halogen, and an OC(O)R.sup.70 group, r is an integer from 1 to 50, R.sup.Sip, R.sup.Siq, R.sup.Sir are independently selected from the group consisting of H, a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group, a C.sub.2-30-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OC.sub.1-30-alkyl group, an OC.sub.2-30-alkenyl group, an OC.sub.2-30-alkynyl group, an OC.sub.5-6-cycloalkyl group, an OC.sub.6-10-aryl group, an O-5 to 10 membered heteroaryl group, an OSi(CH.sub.3).sub.3 group, an NR.sup.700R.sup.800 group, a halogen and an OC(O)R.sup.700 group, R.sup.7, R.sup.8, R.sup.70, R.sup.80, R.sup.700 and R.sup.800 are independently selected from the group consisting of H, a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group, a C.sub.2-30-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, and a 5 to 10 membered heteroaryl group, the C.sub.1-30-alkyl group, the C.sub.2-30-alkenyl group and the C.sub.2-30-alkynyl group optionally comprise one to ten substituents selected from the group consisting of a halogen, CN and NO.sub.2, each R.sup.2 is selected from the group consisting of a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group, a C.sub.2-30-alkynyl group, a C.sub.5-12-cycloalkyl group, a C.sub.6-18-aryl group, a 5 to 20 membered heteroaryl group, an OR.sup.21 group, an OC(O)R.sup.21 group, a C(O)OR.sup.21 group, a C(O)R.sup.21 group, an NR.sup.21R.sup.22 group, an NR.sup.21C(O)R.sup.22 group, a C(O)NR.sup.21R.sup.22 group, an N[C(O)R.sup.21][C(O)R.sup.22] group, an SR.sup.21 group, a halogen, CN, an SiR.sup.SisR.sup.SitR.sup.Sin group and OH, R.sup.21 and R.sup.22 and are independently selected from the group consisting of H, a C.sub.1-30-alkyl group, a C.sub.2-30-alkenyl group, a C.sub.2-30-alkynyl group, a C.sub.5-12-cycloalkyl group, a C.sub.6-18-aryl group and a 5 to 20 membered heteroaryl group, the C.sub.1-30-alkyl group, the C.sub.2-30-alkenyl group and the C.sub.2-30-alkynyl group optionally comprise one to ten substituents independently selected from the group consisting of a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, a 5 to 14 membered heteroaryl group, an OR.sup.e group, an OC(O)R.sup.e group, a C(O)OR.sup.e group, a C(O)R.sup.e group, an NR.sup.eR.sup.f group, an NR.sup.eC(O)R.sup.f group, a C(O)NR.sup.eR.sup.f group, an N[C(O)R.sup.e][C(O)R.sup.f] group, an SR.sup.e group, a halogen, CN, an SiR.sup.SisR.sup.SitR.sup.Siu group and NO.sub.2, at least two CH.sub.2-groups, but not adjacent CH.sub.2-groups, of the C.sub.1-30-alkyl group, the C.sub.2-30-alkenyl group and/or the C.sub.2-30-alkynyl group can be replaced by O or S, the C.sub.5-12-cycloalkyl optionally comprises one to six substituents independently selected from the group consisting of a C.sub.1-20-alkyl group, a C.sub.2-20-alkenyl group, a C.sub.2-20-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, a 5 to 14 membered heteroaryl group, an OR.sup.e group, an OC(O)R.sup.e group, a C(O)OR.sup.e group, a C(O)R.sup.e group, an NR.sup.eR.sup.f group, an NR.sup.eC(O)R.sup.f group, a C(O)NR.sup.eR.sup.f group, an N[C(O)R.sup.e][C(O)R.sup.f] group, an SR.sup.e group, a halogen, CN, an SiR.sup.SisR.sup.SitR.sup.Siu group and NO.sub.2, one or two CH.sub.2-groups, but not adjacent CH.sub.2-groups, of the C.sub.5-12-cycloalkyl group can be replaced by O, S, OC(O), CO, an NR.sup.e group or an NR.sup.eCO group, the C.sub.6-18-aryl group and the 5 to 20 membered heteroaryl group optionally comprise one to six substituents independently selected from the group consisting of a C.sub.1-20-alkyl group, a C.sub.2-20-alkenyl group, a C.sub.2-20-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, a 5 to 14 membered heteroaryl group, an OR.sup.e group, an OC(O)R.sup.e group, a C(O)OR.sup.e group, a C(O)R.sup.e group, an NR.sup.eR.sup.f group, an NR.sup.eC(O)R.sup.f group, a C(O)NR.sup.eR.sup.f group, an N[C(O)R.sup.e][C(O)R.sup.f] group, an SR.sup.e group, a halogen, CN, an SiR.sup.SisR.sup.SitR.sup.Siu group and NO.sub.2, R.sup.Sis, R.sup.Sit and R.sup.Siu are independently selected from the group consisting of H, a C.sub.1-20-alkyl group, a C.sub.2-20-alkenyl group, a C.sub.2-20-alkynyl group, a C.sub.5-6-cycloalkyl group, a phenyl group and an OSi(CH.sub.3).sub.3 group, R.sup.e and R.sup.f are independently selected from the group consisting of H, a C.sub.1-20-alkyl group, a C.sub.2-20-alkenyl group, a C.sub.2-20-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, and a 5 to 14 membered heteroaryl group, the C.sub.1-20-alkyl group, the C.sub.2-20-alkenyl group and the C.sub.2-20-alkynyl group optionally comprise one to five substituents selected from the group consisting of a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OR.sup.g group, an OC(O)R.sup.g group, a C(O)OR.sup.g group, a C(O)R.sup.g group, an NR.sup.gR.sup.h group, an NR.sup.gC(O)R.sup.h group, a C(O)NR.sup.gR.sup.h group, an N[C(O)R.sup.g][C(O)R.sup.h] group, an SR.sup.g group, a halogen, CN, and NO.sub.2, the C.sub.5-8-cycloalkyl group optionally comprises one to five substituents selected from the group consisting of a C.sub.1-10-alkyl group, a C.sub.2-10-alkenyl group, a C.sub.2-10-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OR.sup.g group, an OC(O)R.sup.g group, a C(O)OR group, a C(O)R group, an NR.sup.gR.sup.h group, an NR.sup.gC(O)R.sup.h group, a C(O)NR.sup.gR.sup.h group, an N[C(O)R.sup.g][C(O)R.sup.h] group, an SR.sup.g group, a halogen, CN, and NO.sub.2, the C.sub.6-14-aryl group and the 5 to 14 membered heteroaryl group optionally comprise one to five substituents independently selected from the group consisting of a C.sub.1-10-alkyl group, a C.sub.2-10-alkenyl group, a C.sub.2-10-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OR.sup.g group, an OC(O)R group, a C(O)OR.sup.g group, a C(O)R group, an NR.sup.gR.sup.h group, an NR.sup.gC(O)R.sup.h group, a C(O)NR.sup.gR.sup.h group, an N[C(O)R.sup.g][C(O)R.sup.h] group, an SR.sup.g group, a halogen, CN, and NO.sub.2, R.sup.g and R.sup.h are independently selected from the group consisting of H, a C.sub.1-10-alkyl group, a C.sub.2-10-alkenyl group and a C.sub.2-10-alkynyl group, the C.sub.1-10-alkyl group, the C.sub.2-10-alkenyl group and the C.sub.2-10-alkynyl group optionally comprise one to five substituents selected from the group consisting of a halogen, CN and NO.sub.2, each R.sup.100 and R.sup.101 is independently selected from the group consisting of H, a C.sub.1-20-alkyl group, a C.sub.2-20-alkenyl group, a C.sub.2-20-alkynyl group, a C.sub.5-8-cycloalkyl group, a C.sub.6-14-aryl group, and a 5 to 14 membered heteroaryl group; or wherein R.sup.100 and R.sup.101, if attached to a same atom, together with the same atom, form a 5 to 12 membered ring system, the C.sub.1-20-alkyl group, the C.sub.2-20-alkenyl group and the C.sub.2-20-alkynyl group optionally comprise one to five substituents selected from the group consisting of a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OR.sup.q group, an OC(O)R.sup.q group, a C(O)OR.sup.q group, a C(O)R.sup.q group, an NR.sup.qR.sup.r group, an NR.sup.qC(O)R.sup.r group, a C(O)NR.sup.gR.sup.r group, an N[C(O)R.sup.q][C(O)R.sup.r] group, an SR.sup.q group, a halogen, CN, and NO.sub.2, the C.sub.5-8-cycloalkyl group optionally comprises one to five substituents selected from the group consisting of a C.sub.1-10-alkyl group, a C.sub.2-10-alkenyl group, a C.sub.2-10-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OR.sup.q group, an OC(O)R.sup.q group, a C(O)OR.sup.q group, a C(O)R.sup.q group, an NR.sup.qR.sup.r group, an NR.sup.qC(O)R.sup.r group, a C(O)NR.sup.qR.sup.r group, an N[C(O)R.sup.q][C(O)R.sup.r] group, an SR.sup.q group, a halogen, CN, and NO.sub.2, the C.sub.6-14-aryl group and the 5 to 14 membered heteroaryl group optionally comprise one to five substituents independently selected from the group consisting of a C.sub.1-10-alkyl group, a C.sub.2-10-alkenyl group, a C.sub.2-10-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OR.sup.q group, an OC(O)R.sup.g group, a C(O)OR.sup.g group, a C(O)R.sup.g group, an NR.sup.qR.sup.r group, an NR.sup.qC(O)R.sup.r group, a C(O)NR.sup.qR.sup.r group, an N[C(O)R.sup.q][C(O)R.sup.r] group, a SR.sup.q group, a halogen, CN, and NO.sub.2, the 5 to 12 membered ring system optionally comprises one to five substituents selected from the group consisting of a C.sub.1-10-alkyl group, a C.sub.2-10-alkenyl group, a C.sub.2-10-alkynyl group, a C.sub.5-6-cycloalkyl group, a C.sub.6-10-aryl group, a 5 to 10 membered heteroaryl group, an OR.sup.q group, an OC(O)R.sup.g group, a C(O)OR.sup.g group, a C(O)R.sup.g group, an NR.sup.qR.sup.r group, an NR.sup.qC(O)R.sup.r group, a C(O)NR.sup.qR.sup.r group, an N[C(O)R.sup.q][C(O)R.sup.r] group, an SR.sup.q group, a halogen, CN, and NO.sub.2, R.sup.q and R.sup.r are independently selected from the group consisting of H, a C.sub.1-10alkyl group, a C.sub.2-10-alkenyl group and a C.sub.2-10-alkynyl group, the C.sub.1-10-alkyl group, the C.sub.2-10-alkenyl group and the C.sub.2-10-alkynyl group optionally comprise one to five substituents selected from the group consisting of a halogen, CN and NO.sub.2, and m is in a range from 3 to 1000.

6. The polymer of claim 5, consisting of units haing a structure of formula 4 ##STR00087## R.sup.1b is independently defined as R.sup.1a, and m is in a range from 3 to 1000.

7. A process for preparing the polymer of claim 1, the process comprising condensing a tetraone A and a dione B: ##STR00088## wherein Q.sup.a, Q.sup.b, Q.sup.c, Q.sup.d, Ar and Ar are as defined in claim 1.

8. The process of claim 7, wherein: Q.sup.a and Q.sup.b are an NR.sup.1 group, and Q.sup.c and Q.sup.d are O or an NR.sup.1 group.

9. A process for preparing the polymer of claim 5, the process comprising homopolymerizing a tetraone A: ##STR00089##

10. An electronic device comprising the polymer of claim 1.

11. The electronic device of claim 10, wherein the electronic device is an organic field effect transistor.

12. A polymer consisting of units having a formula selected from P1 to P11: ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## wherein: n is an integer from 3 to 1000.

13. polymer consisting of units having a formula selected from P12 to P14: ##STR00096## wherein: m is an integer from 3 to 1000.

Description

EXAMPLES

(1) The scheme for the synthetic route to 1,5-bis(2-decyltetradecyl)-5,7-dihydropyrrolo[2,3-f]indole-2,6(1H,3H)-dione and 1,5-bis(2-decyltetradecyl)-1,5-dihydropyrrolo[2,3-f]indole-2,3,6,7-tetraone is shown below.

(2) ##STR00061## ##STR00062##

Example 1 Synthesis of 1-bromo-2-decyltetradecane (1)

(3) Under argon, triphenylphosphine (27.8 g, 70.5 mmol) was suspended in a flask with DCM (47 ml). The mixtures was cooled to 0 C. before 2-decyltetradecan-1-ol (29.8 ml, 105.8 mmol) was introduced. After 5 minutes stirring, N-bromosuccinimide (18.8 g, 105.8 mmol) was added portion wise to the flask. The reaction mixture immediately turned yellow and continued to darken to orange. The reaction was stirred for 16 hours after which the solvent was removed by vacuum evaporation. The brown residue was diluted with petroleum ether and the solution flushed through a silica plug. The filtrate was evaporated to give a clear oil. Yield: 28.7 g, 98%. .sup.1H NMR (400 MHz, Chloroform-d) 3.44 (d, J=4.7 Hz, 2H), 1.66-1.47 (m, 2H), 1.44-1.15 (m, 40H), 0.88 (t, J=6.6 Hz, 7H). .sup.13C NMR (101 MHz, CDCl.sub.3) 39.72, 39.70, 32.75, 32.10, 29.97, 29.82, 29.77, 29.53, 26.74, 22.86, 14.26.

Example 2 Synthesis of 2-(2-decyltetradecyl)isoindoline-1,3-dione

(4) A solution of 1-bromo-2-decyltetradecane (20.0 g, 48.0 mmol) and potassium phthalimide (9.98 g, 52.8 mmol) in DMF (57.2 ml) was refluxed for 16 hours. The reaction mixture was cooled to room temperature and poured into water. The aqueous phase was extracted with DCM three times. The combined organic phase was washed with 0.2 M KOH, followed by H.sub.2O and NH.sub.4Cl. After drying the organic phase with MgSO.sub.4 and filtering the salt, the solvent was removed under vacuum. The residue was subjected to a silica plug using 10% EtOAc in petroleum ether, the yellow oil (14.4 g, 62%) obtained was used immediately.

Example 3 Synthesis of 2-decyltetradecan-1-amine (2)

(5) 51% Hydrazine hydrate in water (5.00 ml, 3.1 mmol) was introduced to a solution of 2-(2-decyltetradecyl)isoindoline-1,3-dione (14.40 g, 29.80 mmol) in methanol (10 ml) and refluxed for 16 hours. After cooling, the solvent was removed under vacuum before DCM and 10% KOH solution was added to the residue. The phases were separated and the aqueous phase further extracted with DCM three times. The combined organic phase was washed with brine, dried over MgSO.sub.4, filtered and the solvent removed under reduced pressure. Pale yellow oil, yield 10.0 g, 94% was obtained. .sup.1H NMR (400 MHz, Chloroform-d) 3.51 (d, J=5.5 Hz, 2H), 1.54-1.38 (m, 1H), 1.37-1.17 (m, 40H), 0.94-0.78 (m, 6H). .sup.13C NMR (101 MHz, CDCl.sub.3) 150.50, 108.43, 45.34, 41.01, 36.21, 32.06, 31.67, 30.25, 29.82, 29.49, 27.96, 26.92, 22.82, 14.23. MS TOF ES+: calculated 354.4100, [M+H].sup.+, C24H51N, found 354.4111.

Example 4 Synthesis of N,N-bis(2-decyltetradecyl)benzene-1,4-diamine (3)

(6) 1,4-Cyclohexanedione (0.6 g, 5.0 mmol) was dissolved in ethanol and 2-decyltetradecan-1-amine added to the solution. Air was bubbled through the reaction mixture for 2 hours before the solvent was removed under reduced pressure. The red residue was purified on basified silica gel using 3% EtOAc in petroleum ether to yield 1.8 g, 46% brown oil. .sup.1H NMR (400 MHz, Chloroform-d) 6.54 (s, 4H), 3.24-2.71 (m, 4H), 1.57 (s, 2H), 1.26 (s, 80H), 0.88 (t, J=6.7 Hz, 12H). 13C NMR (101 MHz, CDCl3) 141.18, 114.77, 49.07, 37.95, 32.33, 32.09, 30.25, 29.82, 29.52, 26.90, 22.85, 14.27. MS TOF ES+: calculated 781.8278 [M+H].sup.+, C54H104N2, found 781.8269.

Example 5 Synthesis of benzene-1,4-diylbis{[(2-decyltetradecyl)imino]-2-oxoethane-2,1-diyl} diacetate (4)

(7) Triethylamine (0.70 ml, 4.99 mmol) was added to N,N-bis(2-decyltetradecyl)benzene-1,4-diamine (1.77 g, 2.27 mmol) dissolved in dry DCM (22.70 ml) at O C. Acetoxyacetyl chloride (0.54 ml, 4.99 mmol) was injected into the flask drop wise before the reaction was allowed to warm to room temperature and stirred for 16 hours. The reaction was quenched with NaHCO.sub.3 and EtOAc added. The phases were separated and the aqueous phase extracted three times with EtOAc. The combined organic phase was washed with brine dried over MgSO.sub.4, the salts filtered and the solvent removed under pressure to give pale yellow solid, 2.00 g, 96%. 1H NMR (400 MHz, Chloroform-d) 7.32 (s, 4H), 4.33 (s, 4H), 3.64 (d, J=7.0 Hz, 4H), 2.12 (s, 6H), 1.53-1.41 (m, 2H), 1.37-1.02 (m, 80H), 0.94-0.79 (m, 12H). 13C NMR (101 MHz, CDCl3) 170.61, 166.56, 141.13, 129.79, 61.79, 53.41, 36.25, 32.06, 31.23, 30.15, 29.82, 29.75, 29.50, 26.39, 22.83, 20.65, 14.25. MS TOF LD+: C62H112N2O6 [M+H].sup.+ found 980.9.

Example 6 Synthesis of N,N-benzene-1,4-diylbis[N-(2-decyltetradecyl)-2-hydroxyacetamide] (5)

(8) Benzene-1,4-diylbis{[(2-decyltetradecyl)imino]-2-oxoethane-2,1-diyl} diacetate (3.6 g, 3.7 mmol) in THF (200 ml) and MeOH/water mixture (180 ml, 20 ml). The reaction mixture was stirred in the presence of excess K.sub.2CO.sub.3 at room temperature for 16 hours before the salt was filtered off. The mixture was concentrated under reduced pressure and water and ethyl acetate added to the residue. The phases were separated and the aqueous phase is extracted three times with ethyl acetate. The combined organic phases were washed with brine dried over MgSO.sub.4, filtered and the solvent removed in the rotary evaporator to furnish light yellow, 3.1 g, 94%. .sup.1H NMR (400 MHz, Chloroform-d) 7.24 (s, 4H), 3.76 (s, 4H), 3.70 (d, J=7.1 Hz, 4H), 3.47-3.30 (m, 2H), 1.52-1.37 (m, 2H), 1.36-1.04 (m, 80H), 0.86 (t, J=6.7 Hz, 12H). .sup.13C NMR (101 MHz, CDCl.sub.3) 171.98, 140.31, 129.69, 60.73, 53.47, 36.21, 32.04, 31.23, 30.11, 29.77, 29.71, 29.47, 26.38, 22.80, 14.22. MS TOF LD+: C58H108N2O4, [M+H].sup.+ found 898.00.

Example 7 Synthesis of N,N-(1,4-phenylene)bis(N-(2-decyltetradecyl)-2-oxoacetamide) (6)

(9) Under argon atmosphere, oxalyl chloride (0.31 ml, 3.89 mmol) was diluted with DCM (4 ml) and cooled to 78 C. A solution of DMSO (0.28 ml) in DCM (4.2 ml) was added to the reaction flask at 78 C. The reaction flask was stirred for 20 minutes before N,N-benzene-1,4-diylbis[N-(2-decyltetradecyl)-2-hydroxyacetamide] (1.45 g, 1.62 mmol) diluted in 7 ml DCM was injected dropwise into the flask. The reaction mixture turns aqua green. After 1.5 hours at 78 C., trimethylamine (2.26 ml, 16.2 mmol) was added slowly. The reaction was then stirred at 78 C. for 4 hours before it was allowed to warm to room temperature slowly. The reaction was stirred for 16 hours before it was quenched with saturated NaHCO.sub.3 solution. The phases were separated and the aqueous phase extracted three times with DCM. The combined organic phases were dried with MgSO.sub.4, filtered and the solvent removed under vacuum to yield brown oil, 0.61 g, which was used immediately.

Example 8 Synthesis of 1,5-bis(2-decyltetradecyl)-3,7-bis(phenylthio)-5,7-dihydropyrrolo[2,3-f]indole-2,6(1H,3H)-dione (7)

(10) Crude N,N-(1,4-phenylene)bis(N-(2-decyltetradecyl)-2-oxoacetamide) (1.44 g, 1.61 mmol) was diluted with DCM (6 ml) before thiophenol (0.33 ml, 3.23 mml) was added to flask. The reaction mixture was then stirred for 16 hours at room temperature. Following this, TFAA (2.01 ml, 14.50 mmol) was added slowly to the reaction and stirred for 1 hour 30 minutes, after which, BF.sub.3.Et.sub.2O (0.99 ml, 8.05 mmol) was added to the flask cautiously. Following further stirring for 3 hours, the reaction was cooled to 0 C. before it was quenched with NaHCO.sub.3. The aqueous phase was extracted with DCM three times and the organic phases combined and washed with brine and dried over MgSO.sub.4. The solvent was removed under reduced pressure to furnish red/brown residue as the crude product, which was used without further purification. Yield (1.32 g, 76%) MS (TOF ES+): calculated 1077.8244 C70H112N2O2S2, [M+H]+ found 1077.8278.

Example 9 Synthesis of 1,5-bis(2-decyltetradecyl)-1,5-dihydropyrrolo[2,3-f]indole-2,3,6,7-tetraone (9)

(11) Cerium ammonium nitrate (9.48 g, 17.8 mmol) was added to the solution of 1,5-bis(2-decyltetradecyl)-3,7-bis(phenylthio)-5,7-dihydropyrrolo[2,3-f]indole-2,6(1H,3H)-dione (2.40 g, 2.22 mmol) dissolved in a 6:1 ratio of THF/water (42 ml) mixture. Following 30 minutes stirring at room temperature the reaction mixture takes a deep purple colouration. After 3 hours stirring the reaction mixture was reduced under vacuum. The crude residue was purified by column chromatography at a gradient of 3-10% ethyl acetate in petroleum ether 40-60 C. to furnish the titled compound, yield: 300 mg, 15%. .sup.1H NMR (400 MHz, Chloroform-d) 7.12 (s, ArH, 2H), 3.62 (d, J=7.5 Hz, NCH.sub.2, 4H), 1.84 (d, J=9.9 Hz, CH, 2H), 1.40-1.12 (m, CH.sub.2, 80H), 0.88 (t, J=6.7 Hz, CH.sub.3, 12H). .sup.13C NMR (101 MHz, CDCl.sub.3) 183.36, 157.15, 147.85, 123.24, 106.99, 77.16, 45.49, 36.15, 32.06, 31.52, 30.12, 29.79, 29.76, 29.69, 29.47, 26.40, 22.82, 14.25. MS TOF LD+: C58H100N2O4, [M+H].sup.+ found 890.0.

Example 10 Synthesis of 1,5-bis(2-decyltetradecyl)-5,7-dihydropyrrolo[2,3-f]indole-2,6(1H,3H)-dione (8)

(12) 1,5-bis(2-decyltetradecyl)-3,7-bis(phenylthio)-5,7-dihydropyrrolo[2,3-f]indole-2,6(1H,3H)-dione was dissolved in dry THF (37.0 ml) and 0.1 M SmI.sub.2 in THF (40.0 ml, 4.0 mol) added to the solution at room temperature. Following 16 hours, saturated NaHCO.sub.3 (200 ml) was introduced into the reaction mixture and the aqueous phase extracted with ethyl acetate three times. The organic layer was washed with brine, dried over MgSO.sub.4, filtered and the solvent removed under reduced pressure. Purification by column chromatography in 15% ethyl acetate in 40-60 C. petroleum ether afforded 800 mg beige solid; yield: 28%. 1H NMR (400 MHz, Chloroform-d) 6.73 (s, 2H), 3.56 (d, J=7.9 Hz, ArH 4H), 3.54 (s, CH.sub.2, 4H), 1.91-1.76 (m, CH, 2H), 1.24 (s, CH.sub.2, 80H), 0.87 (t, CH.sub.3, J=6.7 Hz, 12H). .sup.13C NMR (101 MHz, CDCl.sub.3) 174.85, 140.24, 123.92, 106.05, 44.85, 36.41, 36.25, 32.06, 31.68, 30.20, 29.81, 29.49, 26.60, 22.83, 14.26. MS TOF LD+: C58H104N2O2 [M+H].sup.+ found 860.9.

Example 11 Polymerization to Give pDPID P1

(13) A microwave vial was charged with 1,5-bis(2-decyltetradecyl)-5,7-dihydropyrrolo[2,3-f]indole-2,6(1H,3H)-dione (8) (50.0 mg, 0.06 mmol), 1,5-bis(2-decyltetradecyl)-1,5-dihydropyrrolo[2,3-f]indole-2,3,6,7-tetraone (9) (51.6 mg, 0.06 mmol), p-toluene sulfonic acid (3.3 mg, 0.02 mmol) and 4 molecular sieves. The vial was sealed and dry toluene (2 ml), already degassed for 30 minutes was injected into the vial. The reaction was heated at 120 C. for 21 hours followed by 10 hours at 180 C. in the dark. The reaction mixture changed colour from blue to red/brown to dark purple over the polymerization period. The crude polymer was precipitated in methanol and purified by Soxhlet extraction with methanol, acetone, and hexane. The hexane fraction was collected and reduced under vacuum and the polymer precipitated into methanol. The polymer was filtered and dried. Yield of P1: 83 mg, 82% dark purple solid. .sup.1H NMR (400 MHz, Chloroform-d) 9.30 (d, J=8.2 Hz, 2H), 8.93 (s, 2H), 7.11 (d, J=8.2 Hz, 2H), 3.75 (dd, J=13.6, 7.3 Hz, 8H), 2.02 (dt, J=12.8, 6.1 Hz, 4H), 1.66-1.12 (m, 150H), 0.91-0.79 (m, J=3.7 Hz, 24H).

(14) M.sub.n=18 400 g/mol, M.sub.w=29 900 g/mol, PDI=1.6

(15) ##STR00063##

Example 12

(16) Fabrication and Electrical Characterization of an Organic Field-Effect Transistor (OFET) Based on Compound P1

(17) Preparation of Back-Contact, Top-Gate FETs

(18) Compound P1 is dissolved at a concentration of 0.75 wt % in toluene. The transistors have been fabricated on a PET-substrate with lithographically prepatterned gold contacts, serving as Source and Drain contact of the FET. Before the deposition of the semiconductor, the substrate been immersed in a 1 wt % solution of 4-methoxybenzenethiol in ethanol for 2 minutes. Afterwards the substrate has been rinsed with ethanol and blown dry using nitrogen. Next, the semiconductor formulation was applied by spin coating (1,000 rpm, 15 seconds). After the coating is completed, the substrate is immediately transferred onto a preheated hotplate and heated for 30 s at 90 C. Next the gate dielectric layer consisting of Cytop CTL-809 M is spincoated on top of the organic semiconductor (1250 rpm, 30 s). After Spincoating, the substrate is again transferred to the hotplate and annealed for another 5 Min at 90 C. The thickness of the dielectric layer is 500 nm measured by profilometer. Finally 50 nm thick shadow-mask patterend gold gate electrodes are deposited by vacuum evaporation to complete FETs in the BCTG-configuration.

(19) Electrical Characterization

(20) The devices obtained are showing n-type characteristics. The mobility is calculated from the root representation of the transfer characteristic curve (solid grey curve) calculated in the saturation region. The slope m is determined from the dashed black line in FIG. 1. The dashed black line in FIG. 1 is fitted to a region of the root representation of the current characteristic ID such that a good correlation to the linear slope of the root representation is obtained. The threshold voltage U.sub.Th can be taken from the intersection of black dashed line in FIG. 1 with the X-axis portion (V.sub.GS).

(21) In order to calculate the electrical properties of the OFET, the following equations are employed:

(22) $\begin{array}{cccc}=\frac{m^2*2L}{C_G*W}& C_G={\mathrm{.Math.}}_0*{\mathrm{.Math.}}_r\frac{1}{d}& U_{\mathrm{Th}}=-1*\frac{m}{b}& \mathrm{ON}\text{/}\mathrm{OFF}=\frac{I_D\max }{I_D\min }\end{array}$
where .sub.0 is the vacuum permittivity of 8.8510.sup.12 As/Vm, .sub.r=2.1 for Cytop, the thickness of the dielectric d=500 nm, and W/L=25.

(23) The following mobility has been calculated for the respective compound:

(24) TABLE-US-00001 Field-effect mobility Threshold voltage ON/OFF Compound [cm.sup.2/Vs] U.sub.TH [V] ratio P1 9E5 15 2E2

(25) FIG. 1 shows a representative transfer characteristics of a FET fabricated from compound P1 with V.sub.GS=10 V to +30 V at 0.5V step size with V.sub.DS=+30V. Drain current (black solid curve), Gate current (dotted grey curve), Square root of drain current (grey solid curve), and fitted slope of square root (dashed black curve).

Example 13

(26) ##STR00064##

(27) Compound 12 was synthesized according to the reference (J. Mater. Chem. A. 2016, 4, 6940-6945), which was used as crude product without purification.

(28) The crude bisisatin 12 (300 mg, 1.13 mmol) and dry K.sub.2CO.sub.3 (660 mg, 4.78 mmol) and the alkyliodide [1639798-42-7] (2.2 g, 3.26 mmol) were dissolved in 10 mL of dry DMF. The reaction mixture was heated to 100 C. for 4 hours. After cooling down, the reaction mixture was poured over 20 mL H.sub.2O. The aqueous layer was extracted with CHCl.sub.3. The organic layers were dried over MgSO.sub.4 and concentrated to yield the crude reside. The crude product was purified by column chromatography on silica gel (CHCl.sub.3:hexane: 2:1) to get the compound 13. Recrystallization with dichloromethane and methanol, collected and dried in vacuum. Total yield: 230 mg (15%). .sup.1H NMR (400 MHz, CDCl3, rt): =7.99 (d, J=8.7 Hz, 2H), 7.67 (d, J=8.6 Hz, 2H), 4.28-4.24 (m, 4H), 1.79-1.74 (m, 4H), 1.59-1.12 (M, 152H), 0.91-0.88 (m, 12H). .sup.13C NMR (100 MHz, CDCl3, rt): =182.76, 158.96, 152.24, 127.21, 120.08, 119.64, 116.27, 42.12, 35.90, 33.46, 33.16, 31.94, 29.99, 29.72, 29.68, 29.37, 26.63, 22.70, 14.12. Calculated: C92H162N2O. 1359.25, Found: [M+H]: 1360.6.

Example 14 Polymerization to Give pDPID P9

(29) ##STR00065##

(30) Compound 14 was synthesized according to ref: J. Am. Chem. Soc. 2014, 136, 2135-2141. Polymer P9: To a vial was added 13 (71.82 mg, 0.053 mmol, 1 equiv) and bisoxindole 14 (10.04 mg, 0.053 mmol, 1 equiv), PTSA (2 mg). The tube was sealed and flushed with Argon, and then 0.5 ml degassed toluene was added. The mixture was thoroughly degassed under Argon for half an hour, and then the argon inlet was removed. The vial was heated at 120 C. for 3 days. After cooling to RT, the polymer was precipitated into methanol, and filtered through a Soxhlet thimble. The polymer was extracted using Soxhlet apparatus with methanol, acetone, hexane and chloroform. The hexane and chloroform fractions were concentrated and precipitated into methanol. The precipitates were filtered and dried under vacuum to afford P9 as a dark solid (59 mg, 73%). GPC (chlorobenzene, 80 C.): Mn: 25.2 KDa, Mw: 44.3 KDa, PDI=1.76. .sup.1H-NMR (TCE-d.sub.2, 403 K, 400 Hz): =9.04 (broad), 7.76 (broad), 4.34 (broad), 2.18-0.85 (m).

Example 15 Polymerization to Give pDPID P10

(31) ##STR00066##

(32) Compound 15 was synthesized according to the ref: Chem. Commun., 2015, 51, 13515. Polymer P10: To a vial was added 13 (52.78 mg, 0.039 mmol, 1 equiv.) and bisoxindole 15 (9.32 mg, 0.039 mmol, 1 equiv), PTSA (2 mg). The tube was sealed and flushed with Argon, and then 0.5 ml degassed toluene was added. The mixture was thoroughly degassed under Argon for half an hour, and then the argon inlet was removed. The vial was heated at 120 C. for 3 days. After cooling to RT, the polymer was precipitated into methanol, and filtered through a Soxhlet thimble. The polymer was extracted using Soxhlet apparatus with methanol, acetone, hexane and chloroform. The hexane and chloroform fractions were concentrated and precipitated into methanol. The precipitates were filtered and dried under vacuum to afford P10 as a dark solid (47 mg, 77%). GPC (chlorobenzene, 80 C.): Mn: 10.5 k, Mw: 15.7 K, PDI: 1.49. .sup.1HNMR (TCE-d2, 403 K, 400 Hz): =9.33 (d), 9.20 (d), 9.10 (d), 8.05-7.94 (m), 7.71 (d), 7.64 (d), 4.41-4.27 (m), 1.98-1.82 (m), 1.38-0.94 (m).

Example 16 Polymerization to Give pDPID P11

(33) ##STR00067##

(34) Compound 16 was synthesized according to the ref: Organic Electronics 37 (2016) 190-196. Polymer P11: To a vial was added 13 (80.95 mg, 0.0595 mmol, 1 equiv.) and bisoxindole 16 (24.39 mg, 0.04 mmol, 1 equiv), PTSA (4 mg). The tube was sealed and flushed with Argon, and then 0.7 ml degassed toluene was added. The mixture was thoroughly degassed under Argon for half an hour, and then the argon inlet was removed. The vial was heated at 120 C. for 3 days. After cooling to RT, the polymer was precipitated into methanol, and filtered through a Soxhlet thimble. The polymer was extracted using Soxhlet apparatus with methanol, acetone, hexane and chloroform. The hexane and chloroform fractions were concentrated and precipitated into methanol. The precipitates were filtered and dried under vacuum to afford P11 as a dark solid (65 mg, 70%). GPC (chlorobenzene, 80 C.): Mn=21.1 K, Mw=31.2 K, PDI=1.48. .sup.1HNMR (TCE-d.sub.2, 403 K, 400 Hz): =8.71 (broad), 8.01 (broad), 7.57 (broad), 4.33 (broad), 2.12-0.76 (m).

Example 17

(35) ##STR00068##

(36) Compound 17 was synthesized according to compound 13 in example 13 with [1044598-79-9] as alkyl iodide instead of [1639798-42-7].

Example 18 Polymerization to Give pDPID P12

(37) ##STR00069##

(38) To a microwave vial was added the respective bisisatin 17 (0.1 mmol, 1.0 e.q.) and then sealed. The sealed vial was degassed via vacuum and then purged with argon for three cycles. Anhydrous degassed toluene was added under argon and then tris(diethylamino)phosphine P(NEt.sub.2).sub.3 (0.22 mmol, 2.2 e.q.) was added to the mixture at room temperature under bubbling of argon. The mixture turned dark green and then the temperature increased to 100 C. After reaction for 3 hours, the reaction mixture turned dark purple and was then poured into methanol. The resulting polymeric precipitate was filtered via thimble and then purified by Soxhlet extraction in a sequence of methanol, hexane, ethyl acetate, and finally chloroform. The chloroform fraction was concentrated by rotary evaporation, suspended in methanol and filtered to afford the polymer as a metallic dark green solid. GPC (Chlorobenzene at 80 C.): M.sub.n=20.2 kDa, M.sub.w=72.5 kDa, PDI=3.59.

Example 19 Synthesis of Thieno[3,2-b]thiophene Bisisatin 23

(39) ##STR00070## ##STR00071##

(40) Compound 18 was synthesized according to the literature: Adv. Mater. 28, 6921-6925 (2016).

(41) Synthesis of Compound 19:

(42) To a mixture of dimethyl thieno[3,2-b]thiophene-3,6-dicarboxylate (18) (0.77 g, 3.0 mmol, 1.0 e.q.) in ethanol/tetrahydrofuran/water (50 mL/50 mL/5 mL) was added sodium hydroxide (1.5 g, 37.5 mmol, 12.5 e.q.). After the reaction mixture was refluxed overnight, the solvent was evaporated under vacuum to about half of its original volume. Water (50 mL) was added to the mixture and the solution was treated with concentrated hydrochloric acid until white precipitates formed. The precipitate was filtered and then washed with water to give thieno[3,2-b]thiophene-3,6-dicarboxylic acid (19) as a white solid which was dried in a vacuum oven and then used in the next step without further purifications (0.61 g, 2.67 mmol, 89% yield).

(43) Synthesis of Compound 20:

(44) Thieno[3,2-b]thiophene-3,6-dicarboxylic acid (19) (0.55 g, 2.4 mmol, 1.0 e.q.), diphenylphosphoryl azide DPPA (0.56 mL, 2.6 mmol, 1.08 e.q.) and triethylamine (0.36 mL, 2.6 mmol, 1.08 e.q.) were combined in anhydrous tert-butanol (4.5 mL) and the resulting mixture was heated to reflux. After reaction overnight, the solution was cooled and then concentrated in vacuum to remove solvent. The residue was taken up in diethyl ether and washed with 5% aqueous citric acid, water and brine, dried with MgSO.sub.4, and concentrated. The crude product was purified by silica gel column chromatography with ethyl acetate/petroleum ether (1:4) as the eluent to give di-tert-butyl thieno[3,2-b]thiophene-3,6-diyldicarbamate (20) as a light brown solid. (0.60 g, 1.61 mmol, 67% yield). .sup.1H NMR (400 MHz, CDCl.sub.3) 7.38 (s, 2H), 6.60 (s, 2H), 1.57 (s, 18H).

(45) Synthesis of Compound 21:

(46) Di-tert-butyl thieno[3,2-b]thiophene-3,6-diyldicarbamate (20) (0.93 g, 2.5 mmol, 1.0 e.q.) was dissolved in DMF (25 mL) and cooled to 0 C. Sodium hydride (0.40 g, 60% dispersion in mineral oil, 10.0 mmol, 4.0 e.q.) was added and the solution was stirred at room temperature for 1 hour. 7-(bromomethyl)pentadecane (2.29 g, 7.5 mmol, 3.0 e.q.) was added to the mixture and the solution was stirred at 80 C. for 3 hours. After the solution cooled to room temperature, the mixture was poured into iced water, followed by extraction with ethyl acetate for three times. The organic layers were combined, washed with water, brine and then dried over MgSO.sub.4, concentrated. The resulting brown oil was purified via silica gel column chromatography with dichloromethane/petroleum ether (1:1) as the eluent to give di-tert-butyl thieno[3,2-b]thiophene-3,6-diylbis((2-hexyldecyl)carbamate) as a light brown oil (21) (1.64 g, 2.0 mmol, 80% yield). .sup.1H NMR (400 MHz, CDCl.sub.3) 7.04 (s, 2H), 3.62 (d, J=7.2 Hz, 4H), 1.58-1.48 (m, 2H), 1.34-1.11 (m, 48H), 0.87 (q, J=6.8 Hz, 12H). .sup.13C NMR (101 MHz, CDCl.sub.3) 154.13, 134.76, 133.70, 119.18, 80.64, 53.38, 36.93, 31.90, 31.77, 31.21, 30.03, 29.68, 29.52, 29.29, 28.15, 26.31, 26.25, 22.66, 22.62, 14.08.

(47) Synthesis of Compound 22:

(48) Di-tert-butylthieno[3,2-b]thiophene-3,6-diylbis((2-hexyldecyl)carbamate) (21) (1.64 g, 2.0 mmol, 1.0 e.q.) was dissolved in dichloromethane (20 mL) and cooled to 0 C. Trifluoroacetic acid (2.7 mL) was added and the reaction mixture was allowed to warm to room temperature and stirred for overnight. The mixture was poured into water, washed with sodium bicarbonate, brine, dried over MgSO.sub.4 and then concentrated to afford N.sup.3,N.sup.6-bis(2-hexyldecyl)thieno[3,2-b]thiophene-3,6-diamine (22) a light brown oil. The product is unstable in air and used immediately without further purifications in the next step (1.1 g, 1.78 mmol, 89% yield). .sup.1H NMR (400 MHz, CDCl.sub.3) 5.97 (s, 2H), 3.53 (s, 2H), 3.10 (d, J=6.1 Hz, 4H), 1.72-1.63 (m, 2H), 1.50-1.16 (m, 48H), 0.91 (t, J=6.6 Hz, 12H).

(49) Synthesis of Compound 23:

(50) N.sup.3,N.sup.6-bis(2-hexyldecyl)thieno[3,2-b]thiophene-3,6-diamine (22) (1.1 g, 1.78 mmol, 1.0 e.q.) in anhydrous dichloromethane (5 mL) was added dropwise to a stirring solution of oxalyl chloride (0.39 mL, 4.63 mmol, 2.6 e.q.) in anhydrous dichloromethane (10 mL) at 0 C. The mixture was allowed to warm to room temperature and stirred for one hour. Triethylamine (2.23 mL, 16.02 mmol, 9.0 e.q.) in anhydrous dichloromethane (5 mL) was added dropwise at room temperature and the solution was stirred for overnight. The mixture was poured into water and then extracted with dichloromethane for three times. The organic layers were combined, washed with water, brine and then dried over MgSO.sub.4, concentrated. The crude product was purified via silica gel column chromatography with dichloromethane/petroleum ether (3:2) as the eluent and then recrystallized with dichloromethane/methanol to the product (23) as a purple solid. .sup.1H NMR (400 MHz, CDCl.sub.3) 3.70 (d, J=7.7 Hz, 4H), 1.87 (q, J=6.4 Hz, 2H), 1.47-1.20 (m, 48H), 0.93-0.86 (m, 12H). 13C NMR (101 MHz, CDCl.sub.3) 173.02, 160.00, 157.06, 134.45, 116.98, 47.23, 38.99, 31.86, 31.73, 31.28, 29.97, 29.64, 29.49, 29.28, 26.24, 26.19, 22.67, 22.64, 14.13, 14.09.

Example 20 Polymerization to Give pDPID P14

(51) ##STR00072##

(52) Polymer P14 was synthesized from compound 23 according to the procedure for polymer P12 in example 18.