Semiconductor materials prepared from bridged bithiazole copolymers

Abstract

The present invention provides semiconducting compounds, oligomers and polymers of formula ##STR00001##
wherein A.sup.1 and A.sup.2 can be the same or different and are S or Se, E is selected from the group consisting of ##STR00002## The compounds, oligomers and polymers of formula of formula (1) are suitable for use in electronic devices such as organic field effect transistors.

Claims

1. An oligomer or polymer of formula ##STR00120## wherein A.sup.1 and A.sup.2 can be the same or different and are S or Se, E is selected from the group consisting of ##STR00121## wherein R.sup.1 is H, halogen, CN, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-20-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl, C.sub.8-10-cycloalkynyl, C.sub.1-30-haloalkyl, monovalent 3 to 12 membered aliphatic heterocyclic residue, X.sup.1R.sup.6, X.sup.2Ar.sup.1, X.sup.2Ar.sup.2Ar.sup.1, X.sup.2Ar.sup.2R.sup.7 or X.sup.2Ar.sup.2Ar.sup.3R.sup.7, wherein X.sup.1 at each occurrence is independently O, [Z.sup.1O].sub.a, [OZ.sup.1].sub.aO, S, [Z.sup.1S].sub.a, [SZ.sup.1].sub.aS, S(O), C(O), C(O)O, C(O)NR.sup.8, C(O)S, O(CO), S(CO), NR.sup.8C(O) or NR.sup.8, wherein Z.sup.1 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, a at each occurrence is independently an integer from 1 to 10 and R.sup.8 at each occurrence is independently H, C.sub.1-20-alkyl, or Z.sup.2C.sub.6-14-aryl, wherein Z.sup.2 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, R.sup.6 at each occurrence is independently C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl, X.sup.2 at each occurrence is independently Z.sup.3OZ.sup.4, Z.sup.3SZ.sup.4, S(O), C(O), C(O)O, (CO)NR.sup.9, C(O)S, O(CO), S(CO), NR.sup.9C(O), NR.sup.9, Z.sup.3SiR.sup.9.sub.2Z.sup.4, C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond, wherein Z.sup.3 and Z.sup.4 at each occurrence are independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, and R.sup.9 at each occurrence is independently H, C.sub.1-20-alkyl, or Z.sup.5C.sub.6-14-aryl, wherein Z.sup.5 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, Ar.sup.1 at each occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 5 substituents R.sup.a, wherein each R.sup.a is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, Ar.sup.2 and Ar.sup.3 at each occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R.sup.b, wherein each R.sup.b is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and R.sup.7 at each occurrence is independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-halaolkyl, C.sub.1-20-alkoxy, X.sup.3Ar.sup.4, X.sup.3Ar.sup.5Ar.sup.4, X.sup.3Ar.sup.5R.sup.10, or X.sup.3Ar.sup.5Ar.sup.6R.sup.10, wherein X.sup.3 at each occurrence is independently Z.sup.6OZ.sup.7, Z.sup.6SZ.sup.7, S(O), C(O), C(O)O, (CO)NR.sup.11, C(O)S, O(CO), S(CO), NR.sup.11C(O), NR.sup.11, Z.sup.6SiR.sup.11.sub.2Z.sup.7, C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond, wherein Z.sup.6 and Z.sup.7 at each occurrence are independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, and R.sup.11 at each occurrence is independently H, C.sub.1-20-alkyl or Z.sup.8C.sub.6-14-aryl, wherein Z.sup.8 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, Ar.sup.4 at each occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 5 substituents R.sup.c, wherein each R.sup.c is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, Ar.sup.5 and Ar.sup.6 at each occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R.sup.d, wherein each R.sup.d is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and R.sup.10 at each occurrence is independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy, R.sup.3, R.sup.4 and R.sup.5 can be the same or different and are H, halogen, CN, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-20-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl, C.sub.8-10-cycloalkynyl, C.sub.1-30-haloalkyl, monovalent 3 to 12 membered aliphatic heterocyclic residue, X.sup.4R.sup.12, X.sup.5Ar.sup.7, X.sup.5Ar.sup.8Ar.sup.7, X.sup.5Ar.sup.8R.sup.13 or X.sup.5Ar.sup.8Ar.sup.9R.sup.13, wherein X.sup.4 at each occurrence is independently [Z.sup.9O].sub.b, [Z.sup.9S].sub.b, S(O), C(O), C(O)O, C(O)NR.sup.14 or C(O)S, wherein Z.sup.9 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, b at each occurrence is independently an integer from 1 to 10 and R.sup.14 at each occurrence is independently H, C.sub.1-20-alkyl, or Z.sup.10C.sub.6-14-aryl, wherein Z.sup.10 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, R.sup.12 at each occurrence is independently C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl, X.sup.5 at each occurrence is independently Z.sup.11OZ.sup.12, Z.sup.11SZ.sup.12, S(O), C(O), C(O)O, (CO)NR.sup.15, C(O)S, Z.sup.11SiR.sup.15.sub.2Z.sup.12, C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond, wherein Z.sup.11 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, Z.sup.12 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, and R.sup.15 at each occurrence is independently H, C.sub.1-20-alkyl, or Z.sup.13C.sub.6-14-aryl, wherein Z.sup.13 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6 haloalkylene or a covalent bond, Ar.sup.7 at each occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 5 substituents R.sup.e, wherein each R.sup.e is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, Ar.sup.8 and Ar.sup.9 at each occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R.sup.f, wherein each R.sup.f is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl and R.sup.13 at each occurrence is independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl, C.sub.1-20-alkoxy, X.sup.6Ar.sup.10, X.sup.6Ar.sup.11Ar.sup.10, X.sup.6Ar.sup.11R.sup.16, or X.sup.6Ar.sup.11Ar.sup.12R.sup.17, wherein X.sup.6 at each occurance is independently Z.sup.14OZ.sup.15, Z.sup.14SZ.sup.15, S(O), C(O), C(O)O, (CO)NR.sup.18, C(O)S, O(CO), S(CO), NR.sup.18C(O), NR.sup.18, Z.sup.14SiR.sup.18.sub.2Z.sup.15, C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond, wherein Z.sup.14 and Z.sup.15 at each occurrence are independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, and R.sup.18 at each occurrence is independently H, C.sub.1-20-alkyl or Z.sup.16C.sub.6-14-aryl, wherein Z.sup.16 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, Ar.sup.10 at each occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 5 substituents R.sup.g, wherein each R.sup.g is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, Ar.sup.11 and Ar.sup.12 at each occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R.sup.h, wherein each R.sup.h is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl and R.sup.17 at each occurrence is independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20alkoxy, R.sup.19 is O or C(CN).sub.2, and R.sup.20 and R.sup.21 are the same or different and are R.sup.22 or CN, wherein R.sup.22 has the same meaning as R.sup.1, G.sup.1 and G.sup.2 are the same or different and are phenylene or a monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue, which phenylene and monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue are optionally substituted with 1 to 4 substituents R.sup.i, wherein each R.sup.i is independently selected from the group consisting of halogen, CN, NO.sub.2, OH, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, Z.sup.17OC.sub.1-30-alkyl, Z.sup.17SC.sub.1-30-alkyl, Z.sup.17C.sub.3-10-cycloalkyl, Z.sup.17C.sub.5-10-cycloalkenyl, Z.sup.17C.sub.8-10-cycloalkynyl, Z.sup.17C.sub.6-14-aryl, Z.sup.17-monovalent 3 to 12 membered aliphatic heterocyclic residue and Z.sup.17-monovalent 5 to 14 membered aromatic heterocyclic residue, wherein C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl, C.sub.8-10-cycloalkynyl, C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R.sup.j, wherein each R.sup.j is independently selected from the group consisting of haloagen, CN, NO.sub.2, *O, OH, NH.sub.2, NH(C.sub.1-20-alkyl), N(C.sub.1-20-alkyl).sub.2, N(C.sub.1-20-alkyl)-C.sub.6-14-aryl, N(C.sub.6-14-aryl).sub.2, S(O).sub.mH, S(O).sub.mC.sub.1-20-alkyl, S(O).sub.2OH, S(O).sub.mOC.sub.1-20-alkyl, S(O).sub.mOC.sub.6-14-aryl, CHO, C(O)C.sub.1-20-alkyl, C(O)C.sub.6-14-aryl, C(O)OH, C(O)OC.sub.1-20-alkyl, C(O)OC.sub.6-14-aryl, C(O)NH.sub.2, C(O)NHC.sub.1-20-alkyl, C(O)N(C.sub.1-20-alkyl).sub.2, C(O)NHC.sub.6-14aryl, C(O)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl, C(O)N(C.sub.6-14-aryl).sub.2, C(S)NH.sub.2, C(S)NHC.sub.1-20-alkyl, C(S)N(C.sub.1-20-alkyl).sub.2, C(S)N(C.sub.6-14-aryl).sub.2, C(S)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl, C(S)NHC.sub.6-14-aryl, S(O).sub.mNH.sub.2, S(O).sub.mNH(C.sub.1-20-alkyl), S(O).sub.mN(C.sub.1-20-alkyl).sub.2, S(O).sub.mNH(C.sub.6-14-aryl), S(O).sub.mN(C.sub.1-20-alkyl)-C.sub.6-14-aryl, S(O).sub.mN(C.sub.6-14-aryl).sub.2, SiH.sub.3, SiH(C.sub.1-20-alkyl).sub.2, SiH.sub.2(C.sub.1-20-alkyl) and Si(C.sub.1-20-alkyl).sub.3, and wherein C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl, C.sub.8-10-cycloalkynyl, C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R.sup.k, wherein each R.sup.k is independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.1-20-alkoxy, SC.sub.1-20-alkyl, C.sub.1-20-haloalkyl, wherein Z.sup.17 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, and m at each occurrence is independently 0, 1 or 2, L is C.sub.6-24-arylene or a bivalent 5 to 18 membered aromatic heterocyclic residue, wherein C.sub.6-24-arylene and bivalent 5 to 18 membered aromatic heterocyclic residue are optionally substituted with 1 to 4 substituents R.sup.l, wherein each R.sup.l is independently selected from the group consisting of halogen, CN, NO.sub.2, *O, OH, *C(C.sub.1-30-alkyl).sub.2, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, Z.sup.18OC.sub.1-30-alkyl, Z.sup.18SC.sub.1-30-alkyl, Z.sup.18C.sub.3-10-cycloalkyl, Z.sup.18C.sub.5-10-cycloalkenyl, Z.sup.18C.sub.8-10-cycloalkynyl, Z.sup.18C.sub.6-14-aryl, Z.sup.18-monovalent 3 to 12 membered aliphatic heterocyclic residue and Z.sup.18-monovalent 5 to 14 membered aromatic heterocyclic residue, wherein C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl, C.sub.8-10-cycloalkynyl, C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R.sup.m, wherein each R.sup.m is independently selected from the group consisting of halogen, CN, NO.sub.2, *O, OH, NH.sub.2, NH(C.sub.1-20-alkyl), N(C.sub.1-20-alkyl).sub.2, N(C.sub.1-20-alkyl)-C.sub.6-14-aryl, N(C.sub.6-14-aryl).sub.2, S(O).sub.oH, S(O).sub.oC.sub.1-20-alkyl, S(O).sub.2OH, S(O).sub.oOC.sub.1-20-alkyl, S(O).sub.oOC.sub.6-14-aryl, CHO, C(O)C.sub.1-20-alkyl, C(O)C.sub.6-14-aryl, C(O)OH, C(O)OC.sub.1-20-alkyl, C(O)OC.sub.6-14-aryl, C(O)NH.sub.2, C(O)NHC.sub.1-20-alkyl, C(O)N(C.sub.1-20-alkyl).sub.2, C(O)NHC.sub.6-14-aryl, C(O)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl, C(O)N(C.sub.6-14-aryl).sub.2, C(S)NH.sub.2, C(S)NHC.sub.1-20-alkyl, C(S)N(C.sub.1-20-alkyl).sub.2, C(S)N(C.sub.6-14-aryl).sub.2, C(S)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl, C(S)NHC.sub.6-14-aryl, S(O).sub.oNH.sub.2, S(O).sub.oNH(C.sub.1-20-alkyl), S(O).sub.oN(C.sub.1-20-alkyl).sub.2, S(O).sub.oNH(C.sub.6-14-aryl), S(O).sub.oN(C.sub.1-20-alkyl)-C.sub.6-14-aryl, S(O).sub.oN(C.sub.6-14-aryl).sub.2, SiH.sub.3, SiH(C.sub.1-20-alkyl).sub.2, SiH.sub.2(C.sub.1-20-alkyl) and Si(C.sub.1-20-alkyl).sub.3, and wherein C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl, C.sub.8-10-cycloalkynyl, C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R.sup.n, wherein each R.sup.n is independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.1-20-alkoxy, SC.sub.1-20-alkyl, C.sub.1-20-haloalkyl, wherein Z.sup.18 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, and o at each occurrence is independently 0, 1 or 2, or L is ##STR00122## wherein R.sup.23 and R.sup.24 can be the same or different and are H, halogen, CN, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-20-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl, C.sub.8-10-cycloalkynyl, C.sub.1-30-haloalkyl, monovalent 3 to 12 membered aliphatic heterocyclic residue, X.sup.7R.sup.25, X.sup.8Ar.sup.13, X.sup.8Ar.sup.14Ar.sup.13, X.sup.8Ar.sup.14R.sup.26 or X.sup.8Ar.sup.14Ar.sup.15R.sup.26, wherein X.sup.7 at each occurrence is independently O, [Z.sup.19O].sub.c, [OZ.sup.19].sub.cO, S, [Z.sup.19S].sub.c, [SZ.sup.19].sub.cS, S(O), C(O), C(O)O, C(O)NR.sup.27, C(O)S, O(CO), S(CO), NR.sup.27C(O) or NR.sup.27, wherein Z.sup.19 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, c at each occurrence is independently an integer from 1 to 10 and R.sup.27 at each occurrence is independently H, C.sub.1-20-alkyl, or Z.sup.20C.sub.6-14-aryl, wherein Z.sup.20 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, R.sup.25 at each occurrence is independently C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl, X.sup.8 at each occurrence is independently Z.sup.21OZ.sup.22, Z.sup.21SZ.sup.22, S(O), C(O), C(O)O, (CO)NR.sup.28, C(O)S, O(CO), S(CO), NR.sup.28C(O), NR.sup.28, Z.sup.21SiR.sup.28.sub.2Z.sup.22, C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond, wherein Z.sup.21 and Z.sup.22 at each occurrence are independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, and R.sup.28 at each occurrence is independently H, C.sub.1-20-alkyl, or Z.sup.23C.sub.6-14-aryl, wherein Z.sup.23 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, Ar.sup.12 at each occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic residue, each optionally substituted with 1 to 5 substituents R.sup.o, wherein each R.sup.o is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, Ar.sup.14 and Ar.sup.15 at each occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R.sup.p, wherein each R.sup.p is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and R.sup.26 at each occurrence is independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl, C.sub.1-20-alkoxy, X.sup.9Ar.sup.16, X.sup.9Ar.sup.17Ar.sup.16, X.sup.9Ar.sup.17R.sup.29, or X.sup.9Ar.sup.17Ar.sup.18R.sup.29, wherein X.sup.9 at each occurrence is independently Z.sup.24OZ.sup.25, Z.sup.24SZ.sup.25, S(O), C(O), C(O)O, (CO)NR.sup.30, C(O)S, O(CO), S(CO), NR.sup.30C(O), NR.sup.30, Z.sup.24SiR.sup.30.sub.2Z.sup.25, C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond, wherein Z.sup.24 and Z.sup.25 at each occurrence are independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, and R.sup.30 at each occurrence is independently H, C.sub.1-20-alkyl or Z.sup.26C.sub.6-14-aryl, wherein Z.sup.26 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, Ar.sup.16 at each occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 5 substituents R.sup.q, wherein each R.sup.q is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, Ar.sup.17 and Ar.sup.18 at each occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R.sup.r, wherein each R.sup.r is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and R.sup.29 at each occurrence is independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy, q and s are the same or different and are 0, 1, 2, 3, 4 or 5, r is 0, 1 or 2, and n is an integer from 2 to 10,000.

2. The oligomer or polymer of formula (1) of claim 1 wherein E is ##STR00123##

3. An oligomer or polymer of formula (1) ##STR00124## wherein A.sup.1 and A.sup.2 can be the same or different and are S or Se, E is selected from the group consisting of ##STR00125## wherein R.sup.1 is H, halogen, CN, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl, C.sub.8-10cycloakynyl, C.sup.1-30-haloalkyl, monovalent 3 to 12 membered aliphatic heterocyclic residue, X.sup.1R.sup.6, X.sup.2Ar.sup.1, X.sup.2Ar.sup.2Ar.sup.1, X.sup.2Ar.sup.2R.sup.7 or X.sup.2Ar.sup.2Ar.sup.3R.sup.7, wherein X.sup.1 at each occurrence is independently O, [Z.sup.1O].sub.a, [OZ.sup.1].sub.aO, S, [Z.sup.1S].sub.a, [SZ.sup.1].sub.aS, S(O), C(O), C(O)O, C(O)NR.sup.8, C(O)S, O(CO), S(CO), NR.sup.8C(O) or NR.sup.8, wherein Z.sup.1 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, a at each occurrence is independently an integer from 1 to 10 and R.sup.8 at each occurrence is independently H, C.sub.1-20-alkyl, or Z.sup.2C.sub.6-14-aryl, wherein Z.sup.2 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, R.sup.6 at each occurrence is independently C.sub.1-30-alkyl, C.sub.2-30alkenyl or C.sub.1-30-haloalkyl, X.sup.2 at each occurrence is independently Z.sup.3OZ.sup.4, Z.sup.3SZ.sup.4, S(O), C(O), C(O)O, (CO)NR.sup.9, C(O)S, O(CO), S(CO), NR.sup.9C(O), NR.sup.9, Z.sup.3SiR.sup.9.sub.2Z.sup.4, C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond, wherein Z.sup.3 and Z.sup.4 at each occurrence are independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, and R.sup.9 at each occurrence is independently H, C.sub.1-20-alkyl, or Z.sup.5C.sub.6-14-aryl, wherein Z.sup.5 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, Ar.sup.1 at each occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 5 substituents R.sup.a, wherein each R.sup.a is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, Ar.sup.2 and Ar.sup.3 at each occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue each optionally substituted with 1 to 4 substituents R.sup.b, wherein each R.sup.b is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl and R.sup.7 at each occurrence is independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl, C.sub.1-20-alkoxy, X.sup.3Ar.sup.4, X.sup.3Ar.sup.5Ar.sup.4, X.sup.3Ar.sup.5R.sup.10, or X.sup.3Ar.sup.5Ar.sup.6R.sup.10, wherein X.sup.3 at each occurrence is independently Z.sup.6OZ.sup.7, Z.sup.6SZ.sup.7, S(O), C(O), C(O)O, (CO)NR.sup.11, C(O)S, O(CO), S(CO), NR.sup.11C(O), NR.sup.11, Z.sup.6SiR.sup.11.sub.2Z.sup.7, C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond, wherein Z.sup.6 and Z.sup.7 at each occurrence are independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, and R.sup.11 at each occurrence is independently H, C.sub.1-20-alkyl or Z.sup.8C.sub.6-14aryl, wherein Z.sup.8 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, Ar.sup.4 at each occurrence is independently C.sub.6-14-aryl movalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 5 substituents R.sup.c, wherein each R.sup.c is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, Ar.sup.5 and Ar.sup.6 at each occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R.sup.d, wherein each R.sup.d is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and R.sup.10 at each occurrence is independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy, R.sup.4 and R.sup.5 can be the same or different and are H, halogen, CN, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-20-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl, C.sub.8-10-cycloalkynyl, C.sub.1-30-haloalkyl, monovalent 3 to 12 membered aliphatic heterocyclic residue, X.sup.4R.sup.12, X.sup.5Ar.sup.7, X.sup.5Ar.sup.8Ar.sup.7, X.sup.5Ar.sup.8R.sup.13 or X.sup.5Ar.sup.8Ar.sup.9R.sup.13, wherein X.sup.4 at each occurrence is independently [Z.sup.9O].sub.b, [Z.sup.9S].sub.b, S(O), C(O), C(O)O, C(O)NR.sup.14 or C(O)S, wherein Z.sup.9 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, b at each occurrence is independently an integer from 1 to 10 and R.sup.14 at each occurrence is independently H, C.sub.1-20-alkyl, or Z.sup.10C.sub.6-14-aryl, wherein Z.sup.10 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, R.sup.12 at each occurrence is independently C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl, X.sup.5 at each occurrence is independently Z.sup.11OZ.sup.12, Z.sup.11SZ.sup.12, S(O), C(O), C(O)O, (CO)NR.sup.15, C(O)S, Z.sup.11SiR.sup.15.sub.2Z.sup.12, C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond, wherein Z.sup.11 at each occurrence is independently C.sub.1-6alkylene, C.sub.2-6alkenylene or C.sub.1-6-haloalkylene, Z.sup.12 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, and R.sup.15 at each occurrence is independently H, C.sub.1-20-alkyl, or 13 Z.sup.13C.sub.6-14-aryl, wherein Z.sup.13 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6alkenylene, C.sub.1-6-haloalkylene or a covalent bond, Ar.sup.7 at each occurrence is independently C.sub.6-14aryl or monovalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 5 substituents R.sup.e,wherein each R.sup.e is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, Ar.sup.8 and Ar.sup.9 at each occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R.sup.f, wherein each R.sup.f is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl and R.sup.13 at each occurrence is independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl, C.sub.1-20-alkoxy, X.sup.6Ar.sup.10, X.sup.6Ar.sup.11Ar.sup.10, X.sup.6Ar.sup.11R.sup.16, or X.sup.6Ar.sup.11Ar.sup.12R.sup.17, wherein X.sup.6 at each occurrence is independently Z.sup.14OZ.sup.15, Z.sup.14SZ.sup.15, S(O), C(O), C(O)O, (CO)NR.sup.18, C(O)S, O(CO), S(CO), NR.sup.18C(O), NR.sup.18, Z.sup.14SiR.sup.18.sub.2Z.sup.15, C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond, wherein Z.sup.14 and Z.sup.15 at each occurrence are independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, and R.sup.18 at each occurrence is independently H, C.sub.1-20-alkyl or Z.sup.16C.sub.6-14-aryl, wherein Z.sup.16 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6alkenylene, C.sub.1-6-haloalkylene or a covalent bond, Ar.sup.10 at each occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 5 substituents R.sup.g, wherein each R.sup.g is independently selected from the group consisting of halogen, CN, C.sub.1-6alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, Ar.sup.11 and Ar.sup.12 at each occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R.sup.h, wherein each R.sup.h is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl and R.sup.17 at each occurrence is independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy, R.sup.19 is O or C(CN).sub.2, and R.sup.20 and R.sup.21 are the same or different and are R.sup.22 or CN, wherein R.sup.22 has the same meaning as R.sup.1, G.sup.1 and G.sup.2 are same or different and are phenylene or a monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue, which phenylene and monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue are optionally substituted with 1 to 4 substituents R.sup.i, wherein each R.sup.i is independently selected from the group consisting of halogen, CN, NO.sub.2, OH, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, Z.sup.17OC.sub.1-30-alkyl, Z.sup.17C.sub.1-30-alkyl, Z.sup.17C.sub.3-10-cycloalkyl, Z.sup.17C.sub.5-10-cycloalkenyl, Z.sup.17C.sub.8-10-cycloalkynyl, Z.sup.17C.sub.6-14-aryl, Z.sup.17-monovalent3 to 12 membered aliphatic heterocyclic residue and Z.sup.17-monovalent 5 to 14 membered aromatic heterocyclic residue, wherein C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl, C.sub.8-10-cycloalkynyl, C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R.sup.j, wherein each R.sup.j is independently selected from the group consisting of halogen, CN, NO.sub.2, *O, OH, NH.sub.2, NH(C.sub.1-20-alkyl), N(C.sub.1-20-alkyl).sub.2, N(C.sub.1-20-alkyl)-C.sub.6-14-aryl, N(C.sub.6-14-aryl).sub.2, S(O).sub.mH, S(O).sub.mC.sub.1-20-alkyl, S(O).sub.2OH, S(O).sub.mOC.sub.1-20-alkyl, S(O).sub.mOC.sub.6-14-aryl, CHO, C(O)C.sub.1-20-alkyl, C(O)C.sub.6-14-aryl, C(O)OH, C(O)OC.sub.1-20-alkyl, C(O)OC.sub.6-14-aryl, C(O)NH.sub.2, C(O)NHC.sub.1-20-alkyl, C(O)N(C.sub.1-20-alkyl).sub.2, C(O)NHC.sub.6-14-aryl, C(O)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl, C(O)N(C.sub.6-14-aryl).sub.2, C(S)NH.sub.2, C(S)NHC.sub.1-20-alkyl, C(S)N(C.sub.1-20-alkyl).sub.2,C(S)N(C.sub.6-14-aryl).sub.2, C(S)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl, C(S)NHC.sub.6-14-aryl, S(O).sub.mNH.sub.2, S(O).sub.mNH(C.sub.1-20-alkyl), S(O).sub.mN(C.sub.1-20-alkyl).sub.2, S(O).sub.mNH(C.sub.6-14aryl), S(O).sub.mN(C.sub.1-20-alkyl)-C.sub.6-14-aryl, S(O).sub.mN(C.sub.6-14aryl).sub.2, SiH.sub.3, SiH(C.sub.1-20-alkyl).sub.2, SiH.sub.2(C.sub.1-20-alkyl) and Si(C.sub.1-20-alkyl).sub.3, and wherein C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl, C.sub.8-10-cycloalkynyl, C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R.sup.k, wherein each R.sup.k is independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.1-20-alkoxy, SC.sub.1-20-alkyl, C.sub.1-20-haloalkyl, wherein Z.sup.17 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, and m at each occurrence is independently 0, 1 or 2, L is C.sub.6-24-arylene or a bivalent 5 to 18 membered aromatic heterocyclic residue, wherein C.sub.6-24-arylene and bivalent 5 to 18 membered aromatic heterocyclic residue are optionally substituted with 1 to 4 substituents R.sup.l, wherein each R.sup.l is independently selected from the group consisting of halogen, CN, NO.sub.2, *O, OH, *C(C.sub.1-30-alkyl).sub.2, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, Z.sup.18OC.sub.1-30-alkyl, Z.sup.18SC.sub.1-30-alkyl, Z.sup.18C.sub.3-10-cycloalkyl, Z.sup.18C.sub.5-10-cycloalkenyl, Z.sup.18C.sub.8-10-cycloalkynyl, Z.sup.18C.sub.6-14-aryl, Z.sup.18-monovalent 3 to 12 membered aliphatic heterocyclic residue and Z.sup.18-monovalent 5 to 14 membered aromatic heterocyclic residue, wherein C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl, C.sub.8-10-cycloalkynyl, C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R.sup.m, wherein each R.sup.m is independently selected from the group consisting of halogen, CN, NO.sub.2, *O, OH, NH.sub.2, NH(C.sub.1-20-alkyl), N(C.sub.1-20-alkyl).sub.2, N(C.sub.1-20-alkyl)-C.sub.6-14-aryl, N(C.sub.6-14-aryl).sub.2, S(O).sub.oH, S(O).sub.oC.sub.1-20-alkyl, S(O).sub.2OH, S(O).sub.oOC.sub.1-20-alkyl, S(O).sub.oOC.sub.6-14-aryl, CHO, C(O)C.sub.1-20-alkyl, C(O)C.sub.6-14-aryl, C(O)OH, C(O)OC.sub.1-20-alkyl, C(O)OC.sub.6-14-aryl, C(O)NH.sub.2, C(O)NHC.sub.1-20-alkyl, C(O)N(C.sub.1-20-alkyl).sub.2, C(O)NHC.sub.6-14-aryl, C(O)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl, C(O)N(C.sub.6-14-aryl).sub.2, C(S)NH.sub.2, C(S)NHC.sub.1-20alkyl, C(S)N(C.sub.1-20-alkyl).sub.2, C(S)N(C.sub.6-14-aryl).sub.2, C(S)N(C.sub.1-20-alkyl)-C.sub.6-14-aryl, C(S)NHC.sub.6-14-aryl, S(O).sub.oNH.sub.2, S(O).sub.oNH(C.sub.1-20-alkyl), S(O).sub.oN(C.sub.1-20-alkyl).sub.2, S(O).sub.oNH(C.sub.6-14-aryl), S(O).sub.oN(C.sub.1-20-alkyl)-C.sub.6-14-aryl, S(O).sub.oN(C.sub.6-14-aryl).sub.2, SiH.sub.3, SiH(C.sub.1-20-alkyl).sub.2, SiH.sub.2(C.sub.1-20-alkyl) and Si(C.sub.1-20-alkyl).sub.3, and wherein C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl, C.sub.8-10-cycloalkynyl, C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R.sup.n, wherein each R.sup.n is independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.1-20-alkoxy, SC.sub.1-20-alkyl, C.sub.1-20-haloalkyl, wherein Z.sup.18 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, and o at each occurrence is independently 0, 1 or 2, or L is ##STR00126## wherein R.sup.23 and R.sup.24 can be the same or different and are H, halogen, CN, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-20-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl, C.sub.8-10-cycloalkynyl, C.sub.1-30-haloalkyl, monovalent 3 to 12 membered aliphatic heterocyclic residue, X.sup.7R.sup.25, X.sup.8Ar.sup.13, X.sup.8Ar.sup.14Ar.sup.13, X.sup.8Ar.sup.14R.sup.26 or X.sup.8Ar.sup.14Ar.sup.15R.sup.26, wherein X.sup.7 at each occurrence is independently O, [Z.sup.19O].sub.c, [OZ.sup.19].sub.cO, S, [Z.sup.19S].sub.c, [SZ.sup.19].sub.cS, S(O), C(O), C(O)O, C(O)NR.sup.27, C(O)S, O(CO), S(CO), NR.sup.27C(O) or NR.sup.27, wherein Z.sup.19 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, c at each occurrence is independently an integer from 1 to 10 and R.sup.27 at each occurrence is independently H, C.sub.1-20-alkyl, or Z.sup.20C.sub.6-14-aryl, wherein Z.sup.20 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, R.sup.25 at each occurrence is independently C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl, X.sup.8 at each occurrence is independently Z.sup.21OZ.sup.22, Z.sup.21SZ.sup.22, S(O), C(O), C(O)O, (CO)NR.sup.28, C(O)S, O(CO), S(CO), NR.sup.28C(O), NR.sup.28, Z.sup.21SiR.sup.28.sub.2Z.sup.22, C.sub.1-30-alkylene, C.sub.2-30-haloalkenylene, C.sub.1-30-haloalkylene or a covalent bond, wherein Z.sup.21 and Z.sup.22 at each occurrence are independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, and R.sup.28 at each occurrence is independently H, C.sub.1-20-alkyl, or Z.sup.23C.sub.6-14-aryl, wherein Z.sup.23 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, Ar.sup.12 at each occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 5 substituents R.sup.o, wherein each R.sup.o is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, Ar.sup.14 and Ar.sup.15 at each occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R.sup.p, wherein each R.sup.p is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and R.sup.26 at each occurrence is independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl, C.sub.1-20-alkoxy, X.sup.9Ar.sup.16, X.sup.9Ar.sup.17Ar.sup.16, X.sup.9Ar.sup.17R.sup.29, or X.sup.9Ar.sup.17Ar.sup.18R.sup.29, wherein X.sup.9 at each occurrence is independently Z.sup.24OZ.sup.25, Z.sup.24SZ.sup.25, S(O), C(O), C(O)O, (CO)NR.sup.30, C(O)S, O(CO), S(CO), NR.sup.30C(O), NR.sup.30, Z.sup.24SiR.sup.30.sub.2Z.sup.25, C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond, wherein Z.sup.24 and Z.sup.25 at each occurrence are independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, and R.sup.30 at each occurrence is independently H, C.sub.1-20-alkyl or Z.sup.26C.sub.6-14-aryl, wherein Z.sup.26 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, Ar.sup.16 at each occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic heterocyclic residue. each optionally substituted with 1 to 5 substituents R.sup.q, wherein each R.sup.q is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, Ar.sup.17 and Ar.sup.18 at each occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R.sup.r, wherein each R.sup.r is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and R.sup.29 at each occurrence is independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy, q and s are the same or different and are 0, 1, 2, 3, 4 or 5, r is 0, 1 or 2, and n is an integer from 2 to 10,000, wherein R.sup.3 is X.sup.5Ar.sup.7, X.sup.5Ar.sup.8Ar.sup.7, X.sup.5Ar.sup.8R.sup.13 or X.sup.5Ar.sup.8Ar.sup.9R.sup.13, wherein X.sup.5 at each occurrence is a covalent bond, Ar.sup.7 at each occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 5 substituents R.sup.e, wherein each R.sup.e is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, Ar.sup.8 and Ar.sup.9 at each occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R.sup.f, wherein each R.sup.f is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and R.sup.13 at each occurrence is independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy.

4. The oligomer or polymer of formula (1) of claim 1, wherein R.sup.3 is X.sup.5Ar.sup.8R.sup.13, wherein X.sup.5 is a covalent bond, Ar.sup.8 is C.sub.6-14-arylene, and R.sup.13 is C.sub.1-20-alkyl.

5. The oligomer or polymer of formula (1) of claim 1, wherein G.sup.1 and G.sup.2 are the same or different and are phenylene, ##STR00127## or, a monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue selected from the group consisting of ##STR00128## which phenylene or monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue are optionally substituted with 1 to 2 substituents R.sup.i, wherein each R.sup.i is independently selected from the group consisting of C.sub.1-30-alkyl, Z.sup.17OC.sub.1-30-alkyl, Z.sup.17SC.sub.1-30-alkyl, Z.sup.17C.sub.3-10-cycloalkyl, Z.sup.17C.sub.6-14-aryl, Z.sup.17-monovalent 3 to 12 membered aliphatic heterocyclic residue and Z.sup.17-monovalent 5 to 14 membered aromatic heterocyclic residue, wherein C.sub.1-30-alkyl, C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R.sup.j, wherein each R.sup.j is independently selected from the group consisting of halogen, CN and *O, and wherein C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R.sup.k, wherein each R.sup.k is independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.1-20-alkoxy, C.sub.1-20-haloalkyl, wherein Z.sup.17 at each occurrence is independently C.sub.1-6-alkylene, C.sub.1-6-haloalkylene or a covalent bond.

6. The oligomer or polymer of formula (1) of claim 1, wherein G.sup.1 and G.sup.2 are the same or different and are a monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue which monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue is ##STR00129## which monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue is substituted with 1 to 2 substituents R.sup.i, wherein each R.sup.i is independently selected from the group consisting of C.sub.1-30-alkyl and Z.sup.17C.sub.6-14-aryl, wherein C.sub.1-30-alkyl and C.sub.6-14-aryl are optionally substituted with 1 to 4 substituents R.sup.j, wherein each R.sup.j is independently selected from the group consisting of halogen, CN and *O, and wherein C.sub.6-14-aryl is optionally substituted with 1 to 4 substituents R.sup.k, wherein each R.sup.k is independently selected from the group consisting of C.sub.1-20-alkyl and C.sub.1-20-alkoxy, wherein Z.sup.17 at each occurrence is a covalent bond.

7. The oligomer or polymer of formula (1) of claim 1, wherein each R.sup.i is independently C.sub.1-30-alkyl.

8. The oligomer or polymer of formula (1) of claim 1, wherein L is a bivalent 5 to 18 membered aromatic heterocyclic residue, wherein the bivalent 5 to 18 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R.sup.l, wherein each R.sup.l is independently selected from the group consisting of C.sub.1-30-alkyl, Z.sup.18OC.sub.1-30-alkyl, Z.sup.18SC.sub.1-30-alkyl, Z.sup.18C.sub.3-10-cycloalkyl, Z.sup.18C.sub.6-14-aryl, Z.sup.18-monovalent 3 to 12 membered aliphatic heterocyclic residue and Z.sup.18-monovalent 5 to 14 membered aromatic heterocyclic residue, wherein C.sub.1-30-alkyl, C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R.sup.m, wherein each R.sup.m is independently selected from the group consisting of halogen, CN and *O, and wherein C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R.sup.n, wherein each R.sup.n is independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.1-20-alkoxy, C.sub.1-20-haloalkyl, wherein Z.sup.18 at each occurrence is independently C.sub.1-6-alkylene, C.sub.1-6-haloalkylene or a covalent bond, or L is ##STR00130## wherein R.sup.23 and R.sup.24 are the same or different and are H, halogen, CN, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.1-30-haloalkyl, X.sup.7R.sup.25, X.sup.8Ar.sup.13, X.sup.8Ar.sup.14Ar.sup.13, X.sup.8Ar.sup.14R.sup.26 or X.sup.8Ar.sup.14Ar.sup.15R.sup.26, wherein X.sup.7 at each occurrence is independently O, [Z.sup.19O].sub.c, [OZ.sup.19].sub.cO, S, [Z.sup.19S].sub.c or [SZ.sup.19].sub.cS, wherein Z.sup.19 at each occurrence is independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, c at each occurrence is independently an integer from 1 to 10 and R.sup.25 at each occurrence is independently C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl, X.sup.8 at each occurrence is independently Z.sup.21OZ.sup.22, Z.sup.21SZ.sup.22, C.sub.1-30alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond, wherein Z.sup.21 and Z.sup.22 at each occurrence are independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, and Ar.sup.13 at each occurrence is independently C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic residue, each optionally substituted with 1 to 5 substituents R.sup.o, wherein each R.sup.o is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, Ar.sup.14 and Ar.sup.15 at each occurrence are independently C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R.sup.p, wherein each R.sup.p is independently selected from the group consisting of halogen, CN, C.sub.1-6-alkyl, C.sub.1-6-alkoxy and C.sub.1-6-haloalkyl, and R.sup.26 at each occurrence is independently C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy.

9. The oligomer or polymer of formula (1) of claim 1, wherein L is a bivalent 5 to 18 membered aromatic heterocyclic residue selected from the group consisting of ##STR00131## ##STR00132## wherein the bivalent 5 to 18 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R.sup.1, wherein each R.sup.1 is selected from the group consisting of a C.sub.1-30-alkyl, a Z.sup.18OC.sub.1-30-alkyl, a Z.sup.18SC.sub.1-30-alkyl, a Z.sup.18C.sub.3-10-cycloalkyl, a Z.sup.18C.sub.6-14-aryl, a Z.sup.18-monovalent 3 to 12 membered aliphatic heterocyclic residue and a Z.sup.18-monovalent 5 to 14 membered aromatic heterocyclic residue, wherein C.sub.1-30-alkyl, C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R.sup.m, wherein R.sup.m is selected from the group consisting of a halogen, a CN and a *O, C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R.sup.n, wherein R.sup.n is selected from the group consisting of a C.sub.1-20-alkyl, a C.sub.1-20-alkoxy, and a C.sub.1-20-haloalkyl, and Z.sup.18 is C.sub.1-6-alkylene, C.sub.1-6-haloalkylene or a covalent bond, and wherein R.sup.t is hydrogen or C.sub.1-30-alkyl, or L is ##STR00133## wherein R.sup.23 and R.sup.24 are independently H, halogen, CN, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.1-30-haloalkyl, X.sup.7R.sup.25, X.sup.8Ar.sup.13, X.sup.8Ar.sup.14Ar.sup.13, X.sup.8Ar.sup.14R.sup.26 or X.sup.8Ar.sup.14Ar.sup.15R.sup.26, wherein X.sup.7 is O, [Z.sup.19O].sub.c, [OZ.sup.19].sub.cO, S, [Z.sup.19S].sub.c or [SZ.sup.19].sub.cS, wherein Z.sup.19 is C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, and c is an integer of from 1 to 10, R.sup.25 is C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl, X.sup.8 is Z.sup.21OZ.sup.22, Z.sup.21SZ.sup.22, C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond, wherein Z.sup.21 and Z.sup.22 are independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, Ar.sup.13 is C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic residue, each optionally substituted with 1 to 5 substituents R.sup.o, wherein R.sup.o is selected from the group consisting of a halogen, a CN, a C.sub.1-6-alkyl, a C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, Ar.sup.14 and Ar.sup.15 are independently C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R.sup.p, wherein R.sup.p is selected from the group consisting of a halogen, a CN, a C.sub.1-6-alkyl, a C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, and R.sup.26 is C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy.

10. The oligomer or polymer of formula (1) of claim 1, wherein L is ##STR00134## wherein each R.sup.1 is selected from the group consisting of a C.sub.1-30-alkyl, a Z.sup.18OC.sub.1-30-alkyl, a Z.sup.18SC.sub.1-30-alkyl, a Z.sup.18C.sub.3-10-cycloalkyl, a Z.sup.18C.sub.6-14-aryl, a Z.sup.18-monovalent 3 to 12 membered aliphatic heterocyclic residue and a Z.sup.18-monovalent 5 to 14 membered aromatic heterocyclic residue, wherein C.sub.1-30-alkyl, C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R.sup.m, wherein R.sup.m is selected from the group consisting of a halogen, a CN and a *O, C.sub.3-10-cycloalkyl, C.sub.6-14-aryl, monovalent 3 to 12 membered aliphatic heterocyclic residue and monovalent 5 to 14 membered aromatic heterocyclic residue is optionally substituted with 1 to 4 substituents R.sup.n, wherein R.sup.n is selected from the group consisting of a C.sub.1-20-alkyl, a C.sub.1-20-alkoxy, and a C.sub.1-20-haloalkyl, and Z.sup.18 is C.sub.1-6-alkylene, C.sub.1-6-haloalkylene or a covalent bond, or L is ##STR00135## wherein R.sup.23 and R.sup.24 independently H, halogen, CN, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.1-30-haloalkyl, X.sup.7R.sup.25, X.sup.8Ar.sup.13, X.sup.8Ar.sup.14Ar.sup.13, X.sup.8Ar.sup.14R.sup.26 or X.sup.8Ar.sup.14Ar.sup.15R.sup.26, wherein X.sup.7 is O, [Z.sup.19O].sub.c, [OZ.sup.19].sub.c, S, [Z.sup.19S].sub.c or [SZ.sup.19].sub.cS, wherein Z.sup.19 is C.sub.1-6-alkylene, C.sub.2-6-alkenylene or C.sub.1-6-haloalkylene, and c is an integer of from 1 to 10, R.sup.25 is C.sub.1-30-alkyl, C.sub.2-30-alkenyl or C.sub.1-30-haloalkyl, X.sup.8 is Z.sup.21OZ.sup.22, Z.sup.21SZ.sup.22, C.sub.1-30-alkylene, C.sub.2-30-alkenylene, C.sub.1-30-haloalkylene or a covalent bond, wherein Z.sup.21 and Z.sup.22 are independently C.sub.1-6-alkylene, C.sub.2-6-alkenylene, C.sub.1-6-haloalkylene or a covalent bond, Ar.sup.13 is C.sub.6-14-aryl or monovalent 5 to 14 membered aromatic hetrocyclic residue, each optionally substituted with 1 to 5 substituents R.sup.o, wherein R.sup.o is selected from the group consisting of a halogen, a CN, a C.sub.1-6-alkyl, a C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, Ar.sup.14 and Ar.sup.15 are independently C.sub.6-14-arylene or bivalent 5 to 14 membered aromatic heterocyclic residue, each optionally substituted with 1 to 4 substituents R.sup.p, wherein R.sup.p is selected from the group consisting of a halogen, a CN, a C.sub.1-6-alkyl, a C.sub.1-6-alkoxy and a C.sub.1-6-haloalkyl, and R.sup.26 is C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.1-20-haloalkyl or C.sub.1-20-alkoxy.

11. The oligomer or polymer of formula (1) of claim 1, wherein q, r and s are 0 or 1, with the proviso that q, r and s are not all 0 at the same time.

12. The oligomer or polymer of formula (1) of claim 1, wherein n is an integer from 2 to 5000.

13. An electronic device comprising the oligomer or polymer of formula (1) of claim 1.

14. The electronic device of claim 13, wherein the electronic device is an organic field effect transistor.

15. The oligomer or polymer of formula (1) of claim 4, wherein Ar.sup.8 is phenylene.

16. The oligomer or polymer of formula (1) of claim 1, wherein n is an integer from 2 to 1000.

17. The oligomer or polymer of formula (1) of claim 1, wherein n is an integer from 2 to 100.

18. The oligomer or polymer of formula (1) of claim 1, wherein n is an integer from 2 to 30.

19. The oligomer or polymer of formula (1) of claim 1, wherein R.sup.3 is H, halogen, CN, C.sub.2-30-alkenyl, C.sub.2-20-alkynyl, C.sub.3-10-cycloalkyl, C.sub.5-10-cycloalkenyl, C.sub.8-10-cycloalkynyl, C.sub.1-30-haloalkyl, monovalent 3 to 12 membered aliphatic heterocyclic residue, X.sup.4R.sup.12, X.sup.5Ar.sup.7, X.sup.5Ar.sup.8Ar.sup.7, X.sup.5Ar.sup.8R.sup.13 or X.sup.5Ar.sup.8Ar.sup.9R.sup.13.

20. The oligomer or polymer of formula (1) of claim 1, wherein each R.sup.i is independently n-octyl, n-(2-ethyl)hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-icosyl (C.sub.20).

21. The oligomer or polymer of formula (1) of claim 1, wherein each R.sup.i is n-dodecyl.

Description

(1) FIG. 1 shows an organic field effect transistor having a bottom gate bottom contact (BGBC) architecture.

EXAMPLES

Example 1

Preparation of 2,2-dibromo-(5,6-dihexylbenzo[2,1-d;3,4-d]bisthiazole) (2a)

(2) ##STR00113##

Preparation of 4,4-dibromo-5,5-bithiazole (6a)

(3) N-bromosuccinimide (6.35 g, 35.66 mmol, 4 eq.) is added to a stirred homogeneous solution of 5,5-bithiazole (7a) (1.5 g, 8.9 mmol) in anhydrous DMF (125 mL). The reaction mixture is heated at 60 C. for 3 hours. The reaction mixture is washed subsequently with an aqueous solution of 10% sodium bicarbonate (200 mL), extracted with dichloromethane (200 mL), washed with water (3100 mL) and sodium chloride saturated water (100 mL), and dried over anhydrous sodium sulfate. The crude product is re-crystallized from dichloromethane/n-hexane (1:10). Yellowish crystals are obtained. .sup.1H-NMR (d-chloroform) (400 MHz): 8.87 (s, 2H). .sup.13C-NMR (d-chloroform) (400 MHz): 154.8, 129.3, 122.5.

Preparation of 2,2-bis(triisopropylsilyl)-4,4-dibromo-5,5-bithiazole (5a)

(4) 1.84 mL of a 2M solution of lithium diisopropylamide (0.39 g, 3.68 mmol, 2.4 eq.) in THF is added dropwise to a solution of 4,4-dibromo-5,5-bithiazoles (6a) (0.5 g, 1.53 mmol) in anhydrous THF (20 mL) at 78 C. over 10 minutes. The reaction mixture is allowed to stir for 3 hours, and then triisopropylsilyl chloride (0.709 g, 0.79 mL, 3.68 mmol, 2.4 eq.) is added slowly. The reaction mixture is warmed up to room temperature overnight. The reaction mixture is diluted with ethyl acetate (140 mL), and the organic layer is washed with sodium bicarbonate saturated water (70 mL) and sodium chloride saturated water (70 mL), dried over magnesium sulfate and concentrated in vacuo. Column chromatography using gradient solvent from n-hexane to ethyl acetate/n-hexane (5/95) provides a yellow solid. .sup.1H-NMR (d-chloroform) (400 MHz): 2.43-1.5 (m, J=8 Hz, 6H), 1.16-1.18 (d, J=7.6 Hz, 36H). .sup.13C-NMR (d-chloroform) (400 MHz): 172.7, 130.5, 125.1, 18.7, 11.8.

Preparation of 2,2-bis(triisopropylsilyl)-(5,6-dihexylbenzo[2,1-d;3,4-d]bisthiazole) (4a)

(5) A mixture of 5a (0.5 g, 0.783 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.090 g, 0.078 mmol, 0.1 eq.) is degassed 3 times. A solution of vic-bis(pinacolatoboryl)-7-tetradecene (0.456 g, 1.018 mmol, 1.3 eq.), in anhydrous toluene (5 mL) is added, followed by 12 mL of toluene (total 17 mL anhydrous toluene). Subsequently 2.8 mL of degassed aqueous solution of potassium carbonate (0.64 g, 4.70 mmol, 6 eq.) is added. The reaction mixture is stirred and heated at 100 C. overnight. The reaction mixture is allowed to cool to room temperature, and is diluted with ethyl acetate (50 mL). The resulting reaction mixture is washed with ammonium chloride saturated water (50 mL) and the aqueous layer is extracted with ethyl acetate (350 mL). The combined organic layers are washed with sodium chloride saturated water (25 mL), dried over magnesium sulfate, and concentrated in vacuo. Column chromatography using a gradient solvent from n-hexane to ethyl acetate/n-hexane (10/90) provides an off-white solid. .sup.1H-NMR (d-chloroform) (400 MHz): 3.37 (dd, J=8 Hz, 4H), 1.74-1.76 (m, J=8 Hz, 4H), 1.47-1.55 (m, J=8 Hz, 6H), 1.33-1.37 (m, J=8 Hz, 12H), 1.2-1.22 (d, J=8 Hz, 36H), 0.87-0.92 (t, J=7.6 Hz, 6H). LC-MS: 95% purity with m/z 673.4.

Preparation of 2,2-dibromo-(5,6-dihexylbenzo[2,1-d;3,4-d]bisthiazole) (2a)

(6) A solution of bromine (0.34 g, 0.11 mL, 2.11 mmol, 4 eq.) in chloroform (5 mL) containing trichloroacetic acid (7 mg) is added dropwise and slowly to a solution of 4a (0.355 g, 0.527 mmol) in chloroform (8 mL) at 0 C. The reaction mixture is stirred at room temperature for 3 days. The reaction mixture is diluted with dichloromethane (50 mL), washed with an aqueous solution of 20 weight % sodium thiosulfate (50 mL) and with an aqueous solution of 10 weight % sodium bicarbonate (50 mL). Subsequently the organic layer is dried over magnesium sulfate and concentrated in vacuo. Purification by column chromatography (ethyl acetate/n-hexane (10/90)) followed by re-crystallisation from ethanol affords light brown crystals. .sup.1H-NMR (d-chloroform) (400 MHz): 3.17 (dd, J=8 Hz, 4H), 1.66 (m, J=8 Hz, 4H), 1.47 (m, J=8 Hz, 4H), 1.35 (m, J=8 Hz, 8H), 0.92 (t, J=7.6 Hz, 6H). LC-MS: 98% purity with m/z 519. Elemental analysis (calcd): C, 46.34 (46.36); H, 5.06 (5.09).

Example 2

Preparation of poly(benzobisthiazole-cyclopentadithiophene) (1a)

(7) ##STR00114##

(8) Dibromo-benzobisthiazole (2a) (60 mg, 0.116 mmol, 1 eq.), bis(trimethylstannyl)cyclopentadithiophene (3a) (110 mg, 0.116 mmol, 1 eq.), tris(dibenzylidene-acetone)dipalladium(0) (3.2 mg, 0.003 mmol, 3% eq.) and tri-o-tolylphosphine (2.1 mg, 0.007 mmol, 6% eq.) are added into a Schlenk flask and degassed 3 times. Chlorobenzene (4 mL) is added and the reaction mixture is stirred at 100 C. overnight then at 130 C. for 2 days. 2-Bromothiophene (0.01 mL) and 2-tributylstannylthiophene (0.01 mL) are added as end cappers, with 2-bromothiophene added first followed by 2-tributylstannylthiophene 2 hours later. After another 2 hours stirring, the reaction mixture is cooled to room temperature. The reaction mixture is then added dropwise to methanol (200 mL), filtered, and then subjected to Soxhlet extraction with acetone. The polymer is recovered as solid mass and showed Mn=8360 g/mol (Mw=24264 g/mol & PDI=2.92). Elemental analysis (calcd): C, 70.77 (74.48); H, 8.93 (9.63).

Example 3

Preparation of poly(benzobisthiazole-bisthienylethylene) (1b)

(9) ##STR00115##

(10) Dibromo-benzobisthiazole (2a) (55 mg, 0.106 mmol, 1 eq.) prepared as described in example 1, bis(2-trimethylstannyl-4-dodecylthienyl)ethylene (3b) (90.7 mg, 0.106 mmol, 1 eq.), tris(dibenzylideneacetone)dipalladium(0) (2.9 mg, 0.003 mmol, 3% eq.) and tri-o-tolylphosphine (1.9 mg, 0.006 mmol, 6% eq.) are added into a Schlenk flask and degassed 3 times. Chlorobenzene (2 mL) is added and the reaction mixture is stirred at 130 C. for 2 days. 2-Bromothiophene (0.01 mL) and 2-tributylstannylthiophene (0.01 mL) are added as end cappers, with 2-bromothiophene added first followed by 2-tributylstannylthiophene 2 hours later. After another 2 hours stirring, the reaction mixture is cooled to room temperature. The mixture is filtered and the filtrate is concentrated and added dropwise to methanol (200 mL), filtered, and then subjected to Soxhlet extraction with acetone. The polymer is recovered as solid mass and showed Mn=3368 g/mol (Mw=4749 g/mol & D=1.41).

Example 4

Preparation of poly(benzobisthiazole-bithiophene) (1c)

(11) ##STR00116##

Preparation of 2,2-dibromo-(5,6-dimethylbenzo[2,1-d;3,4-d]bisthiazole) (2b)

(12) Dibromo-benzobisthiazole (2b) is prepared in analogy to 2,2-dibromo-(5,6-dihexylbenzo[2,1-d;3,4-d]bisthiazole) (2a) in example 1, except that vic-bis(pinacolatoboryl)-2-butene (with the equivalent of 1.3 eq to the substrate 5a) is used instead of vic-bis(pinacolatoboryl)-7-tetradecene (with the equivalent of 1.3 eq to the substrate 5a).

Preparation of poly(benzobisthiazole-bithiophene) (1c)

(13) Dibromo-benzobisthiazole (2b) (79 mg, 0.209 mmol, 1 eq.) is added as a 4.2 mL chlorobenzene solution into a pre-degassed mixture of bis(2-trimethylstannyl-2-dodecylthiophene) (3c) (173.1 mg, 0.209 mmol, 1 eq.), tris(dibenzylideneacetone)dipalladium(0) (5.7 mg, 0.003 mmol, 3% eq.) and tri-o-tolylphosphine (3.8 mg, 0.006 mmol, 6% eq.). The reaction mixture is stirred at 130 C. for 2 days. After two days of reaction, tris(dibenzylideneacetone)-dipalladium(0) (5.7 mg, 0.003 mmol, 3% eq.) and tri-o-tolylphosphine (3.8 mg, 0.006 mmol, 6% eq.) is added. After four days of reaction, another portion of tris(dibenzylidene-acetone)dipalladium(0) (5.7 mg, 0.003 mmol, 3% eq.) and tri-o-tolylphosphine (3.8 mg, 0.006 mmol, 6% eq.) is added. After total 6 days, the polymerization is stopped by the addition of 2-bromothiophene (0.01 mL) and 2-tributylstannylthiophene (0.01 mL). 2-Bromothiophene is added first followed by 2-tributylstannylthiophene 4 hours later. After another 24 hours stirring, the reaction mixture is cooled to room temperature. The mixture is filtered and the filtrate is concentrated and added dropwise to a methanolic solution of 5 weight % HCl (200 mL). The polymer is filtered and before soxhlet extraction in acetone showed Mn=959 g/mol (Mw=1410 g/mol & D=1.47).

Example 5

Preparation of N-4-decylaniline-2,6-dibromo dithiazolo[2,3-d;3,2-b]pyrrole (2c)

(14) ##STR00117##

Preparation of N-4-decylaniline-2,6-bis(triisoproylsilyl)dithiazolo[2,3-d;3,2-b]pyrrole) (4b)

(15) A mixture of bis(triisopropylsilyl)-dibromobithiazole (5a) (790 mg, 1.237 mmol), tris(dibenzylideneacetone)dipalladium(0) (113 mg, 0.123 mmol, 0.1 eq.), sodium tert-butoxide (200 mg, 2.968 mmol, 2.4 eq.) and rac-BINAP (153 mg, 0.347 mmol, 0.2 eq.) is degassed 3 times. 4-n-Decylaniline (360 mg, 1.546 mmol, 1.25 eq.) in anhydrous toluene (18 mL) is added. The reaction mixture is stirred and heated at 100 C. for 2 days under nitrogen. After the mono-aminated intermediate is formed tris(dibenzylidene-acetone)dipalladium(0) (56 mg, 0.061 mmol, 0.05 eq.) and 0.36 mL of a 10 weight % solution of tri-tert-butylphosphine (24 mg, 0.173 mmol, 0.1 eq.) in n-hexane is added. The reaction mixture is stirred at 100 C. for 2 days under nitrogen. Afterwards the reaction mixture is diluted with ethyl acetate (100 mL). The resulting reaction mixture is washed with ammonium chloride saturated water (100 mL) and the aqueous layer is extracted with ethyl acetate (370 mL). The combined organic layers are washed with sodium chloride saturated water (50 mL), dried over magnesium sulfate, and concentrated in vacuo. Column chromatography using ethyl acetate/n-hexane (2/98) provided off-white solid. .sup.1H-NMR (d-chloroform) (400 MHz): 8.58 (d, J=9.6 Hz, 2H), 7.34 (d, J=8.4 Hz, 2H), 2.28 (dd, J=8 Hz, 2H), 1.65 (m, J=8 Hz, 2H), 1.52-1.46 (m, J=8 Hz, 6H), 1.27 (s, 14H), 1.19-1.21 (d, J=8 Hz, 36H), 0.88 (t, J=7.6 Hz, 3H).

Preparation of N-4-decylaniline-2,6-dibromo dithiazolo[2,3-d;3,2-b]pyrrole (2c)

(16) A solution of bromine (0.16 g, 0.05 mL, 1.01 mmol, 4 eq.) in chloroform (3 mL) containing trichloroacetic acid (4 mg) is slowly and dropwise added to a solution of 4b (0.180 g, 0.253 mmol) in chloroform (4 mL) at 0 C. The reaction mixture is stirred at room temperature for 2 days. The reaction mixture is diluted with dichloromethane (50 mL), washed with an aqueous solution of 20 weight % sodium thiosulfate (50 mL) and an aqueous solution of 10 weight % sodium bicarbonate (50 mL). Subsequently the organic layer is dried over magnesium sulfate and concentrated in vacuo. Purification by column chromatography using n-hexane followed by re-crystallisation from n-hexane affords white flakes. .sup.1H-NMR (d-chloroform) (400 MHz): 7.88 (d, J=8.4 Hz, 2H), 7.35 (d, J=8 Hz, 2H), 2.66 (dd, J=7.6 Hz, 2H), 1.63 (m, J=7.6 Hz, 2H), 1.28 (s, 14H), 0.88 (t, J=7.6 Hz, 3H). LC-MS: 97.2% purity with m/z 556. Elemental analysis (calcd): C, 47.54 (47.58); H, 4.46 (4.54).

Example 6

Preparation of poly(dithiazolopyrrole-bisthienylethylene) (1d)

(17) ##STR00118##

(18) Dibromo-dithiazolopyrrole (2c) (36 mg, 0.065 mmol, 1 eq.) prepared as described in example 5, bis(2-trimethylstannyl-4-dodecylthienyl)ethylene (3d) (55.4 mg, 0.065 mmol, 1 eq.), tris(dibenzylideneacetone)dipalladium(0) (3.6 mg, 0.004 mmol, 6% eq.) and tri-o-tolylphosphine (2.4 mg, 0.008 mmol, 12% eq.) are added into a Schlenk flask and degassed 3 times. Chlorobenzene (1.5 mL) is added and the reaction mixture is stirred at 130 C. for 2 days. After two days of reaction, tris(dibenzylideneacetone)dipalladium(0) (3.6 mg, 0.004 mmol, 6% eq.) and tri-o-tolylphosphine (2.4 mg, 0.008 mmol, 12% eq.) was added. After total reaction of 3 days, the polymerization is stopped by the addition of 2-bromothiophene (0.01 mL) followed by 2-tributylstannylthiophene (0.01 mL) 3 hours later. After another 3 hours stirring, the reaction mixture is cooled to room temperature and added dropwise to methanol (100 mL), filtered, and then subjected to Soxhlet extraction with acetone. The polymer is recovered as solid mass and showed Mn=4305 g/mol (Mw=7571 g/mol & D=1.76).

(19) Measurement of the Ionization Potential of Polymer 1a

(20) The oxidative stability of -conjugated polymers may be contributed by their ionization potential (IP), that is, on the energy of the highest occupied molecular orbital (HOMO) with respect to vacuum. The ionization potential (IP) is also reflected as negative value of the HOMO energy level (E.sub.HOMO) of a molecule, oligomer or polymer,
IP=E.sub.HOMO
and can be measured by cyclic voltammetry (CV).

(21) The HOMO energy levels (E.sub.HOMO) of poly(benzobisthiazole-cyclopentadithiophene) (1a), prepared as described in example 2, and comparative polymer 22a, which is described by Xiao, S; Zhou H.; You, W. in Macromolecules 2008, 41, 5688-5696, are determined by cyclic voltammetry (CV).

(22) ##STR00119##

(23) Cyclic voltamogramms are recorded from thin films of polymer 1a, respectively comparative polymer 22a, drop-casted from 0.5 mg/mL chloroform solutions. A Pt disk is used as a working electrode and Ag/AgCl reference electrode is employed. The measurement is done in tetrabutylammonium tetrafluoroborate as electrolyte and ferrocene/ferrocenium redox couple (Fc/Fc.sup.+) is used as an internal reference, which has a known reduction potential of 4.8 eV. The electrochemical (oxidation and reduction) onset is determined at the position where the current starts to differ from the baseline and the HOMO energy level (E.sub.HOMO) is calculated from the onset oxidation potential (E.sub.Ox), as shown in the equation below:
E.sub.HOMO=(E.sub.Ox+4.8)[eV]

(24) The results are outlined in table 1.

(25) TABLE-US-00001 TABLE 1 polymer E.sub.HOMO [eV] 1a 5.44 22a (comparative) 5.04

(26) As can be derived from table 1, the HOMO energy level (E.sub.HOMO) value of polymer 1a is decreased by 0.4 eV compared to the HOMO energy level (E.sub.HOMO) value of comparative polymer 22a, and thus the ionization potential (IP) and consequently the oxidative stability of polymer 1a is higher than the one of comparative polymer 22a.

(27) Fabrication of an Organic Field-Effect Transistor Using Polymer 1a as Semiconductor

(28) An organic field effect transistor is made in bottom gate bottom contact (BGBC) architecture, as depicted in FIG. 1. Heavily doped Si wafer are used as substrate and gate electrode with 200 nm thermally grown SiO.sub.2 serving as gate dielectric. Source and drain electrode are made of gold which is lithographically patterned. Before semiconductor deposition, the substrate is vapor treated with hexamethyldisilazane (HMDS). The polymer 1a solution is prepared by solubilizing the polymer 1a in 1,2-dichlorobenzene and heating it inside oven until soluble. Subsequently, semiconductor solution deposition of the polymer 1a is done by spin coating (deposition condition: 2000 rpm, 255 acc, 1 minute). The organic field effect transistor is made in ambient environment.

(29) Testing of the Organic Field-Effect Transistor Using Polymer 1a as Semiconductor

(30) The hole mobility (.sub.p), onset voltage (V.sub.on, voltage when the drain current increases abruptly and can be measured), and the on/off ratio of the organic field effect transistor using polymer 1a as semiconductor are determined at room temperature and after annealing at 200 C. for 30 minutes, in order to observe the effect of annealing on the semiconductor performance. The organic field effect transistor is tested in ambient environment. Channel length (L)=5 m, Channel width (W)=350 m, W/L=70. Measurement is performed at: gate voltage (Vg)=sweep from 20 to 90 V, drain voltage (Vd)=90 V,

(31) The results are outlined in table 2.

(32) TABLE-US-00002 TABLE 2 hole mobility .sub.p [cm.sup.2/Vs] V.sub.on [V] On/Off ratio at RT 0.2 10.sup.3 5 2.66 10.sup.4 after annealing at 200 C. 1.06 10.sup.3 5 6.01 10.sup.4