Naphthoindacenodithiophenes and polymers

Abstract

Polymers comprising at least one unit of formula 1 and compounds of the formula 1 wherein, in formulae 1 and 1 n is 0, 1, 2, 3 or 4 m is 0, 1, 2, 3 or 4 X is at each occurrence selected from the group consisting of O, S, Se or Te, Q is at each occurrence selected from the group consisting of C, Si or Ge R is at each occurrence selected from the group consisting of hydrogen, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.5-12-cycloalkyl, C.sub.6-18-aryl, R.sup.2, R.sup.2, R* are at each occurrence independently selected from the group consisting of hydrogen, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.5-12-cycloalkyl, C.sub.6-18-aryl, 5 to 20 membered hetero-aryl, OR.sup.21, OC(O)R.sup.21, C(O)OR.sup.21, C(O)R.sup.21, NR.sup.21.sub.R.sup.22, NR.sup.21C(O)R.sup.22, C(O)NR.sup.21R.sup.22, N[C(O)R.sup.21][C(O)R.sup.22], SR.sup.21, halogen, CN, SiR.sup.SisR.sup.SitR.sup.Siu and OH, L.sup.1 and L.sup.2 are independently from each other and at each occurrence selected from the group consisting of C.sub.6-30-arylene, 5 to 30 membered heteroarylene. ##STR00001##

Claims

1. A polymer comprising a unit of formula 1: ##STR00084## wherein: n is 0, 1, 2, 3, or 4; m is 0, 1, 2, 3, or 4; R is selected from the group consisting of hydrogen, C.sub.1-30-alkyl, and phenyl; L.sup.1 and L.sup.2 are each independently selected from the group consisting of C.sub.6-30-arylene, 5 to 30 membered heteroarylene, ##STR00085## wherein C.sub.6-30-arylene and 5 to 30 membered heteroarylene are optionally substituted with one to six substituents R.sup.3 selected from the group consisting of C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.5-12-cycloalkyl, C.sub.6-18-aryl and 5 to 20 membered heteroaryl, OR.sup.31, OC(O)R.sup.31, C(O)OR.sup.31, C(O)R.sup.31R.sup.32, NR.sup.31C(O)R.sup.32,C(O)NR.sup.31R.sup.32, N[C(O)R.sup.31][C(O)R.sup.32], SR .sup.31, halogen, CN, SiR.sup.SivR.sup.SiwR.sup.Six and OH, wherein ##STR00086## are optionally substituted with one or two substituents R.sup.4 selected from the group consisting of C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.5-12-cycloalkyl, C.sub.6-18-aryl and 5 to 20 membered heteroaryl, C(O)R.sup.41, C(O)NR.sup.41R.sup.42, C(O)OR.sup.41and CN, wherein, in R.sup.31, R.sup.32, R.sup.41, and R.sup.42, are each independently selected from the group consisting of H, C.sub.1-30-alkynyl, C.sub.2-30-alkenyl, C.sub.2-36-alkynyl, C.sub.5-12, -cycloalkyl, C.sub.6-18-aryl and 5 and 20 membered heroaryl, wherein, in R.sup.31, R.sup.32, R.sup.41, are each independently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.2-30-alkenyl and C.sub.2-30-alkynyl C.sub.5-12- cycloalkyl, C.sub.6-18-aryl and 5 to 20 membered heteroaryl, wherein, in R.sup.31, R.sup.32, R.sup.41, and R.sup.42, C.sub.5-12-cycloalkyl is optionally substituted with one to six substituents independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl and C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 14 membered heteroaryl, OR.sup.i, OC(O)R.sup.j, C(O)OR.sup.i, C(O)R.sup.i, NR.sup.iR.sup.j, NR.sup.iC(O)R.sup.j, C(O)NR.sup.iR.sup.j, N[C(O)R.sup.i][C(O)R.sup.j], SR.sup.i, halogen, CN, SiR.sup.SivR.sup.SiwR.sup.Six and NO.sub.2: and one or two CH.sub.2-groups, but not adjacent CH.sub.2-groups, of C.sub.5-12-cycloalkyl are optionally replaced by O, S, OC(O), CO, NR.sup.ior NR.sup.iCO, wherein, in R.sup.31, R.sup.32, R.sup.41, and R.sup.42, C.sub.6-18-aryl and 5 to 20 membered heteroaryl are optionally substituted with one to six substituents independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 14 membered heteroaryl, OR.sup.i, OC(O)R.sup.j, C(O)OR.sup.i, C(O)R.sup.i, NR.sup.iR.sup.j, NR.sup.iC(O)R.sup.j, C(O)NR.sup.iR.sup.j, N[C(O)R.sup.i][C(O)R.sup.j], SR.sup.i, halogen, CN, SiR.sup.sivR.sup.SiwR.sup.Sixand NO.sub.2, wherein, in R.sup.31, R.sup.32, R.sup.41, and R.sup.42, C.sub.1-30-alkyl, C.sub.2-30-alkenyl and C.sub.2-30-alkynyl are optionally substituted with one to ten substituents independently selected from the group consisting of C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 14 membered heteroaryl, OR.sup.i, OC(O)R.sup.j, C(O)OR.sup.i, C(O)R.sup.i, NR.sup.iR.sup.j, NR.sup.iC(O)R.sup.j, C(O)NR.sup.iR.sup.j, N[C(O)R.sup.i][C(O)R.sup.j], SR.sup.i, halogen, CN, SiR.sup.SivR.sup.SiwR.sup.Six and NO.sub.2; and at least two CH.sub.2-groups, but not adjacent CH.sub.2-groups of C.sub.1-30-alkyl, C.sub.2-30-alkenyl and C.sub.2-30-alkynyl are optionally replaced by O or S, wherein, in R.sup.31, R.sup.32, R.sup.41, and R.sup.42, C.sub.5-12-cycloalkyl is optionally substituted with one to six substituents independently selected from the group consisting of C.sub.1-20-alkyl, and C.sub.2-20-alkeynyl and C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 14 membered heteroaryl, OR.sup.i, OC(O)R.sup.j, C(O)OR.sup.i, C(O)R.sup.i, NR.sup.iR.sup.j, NR.sup.iC (O)R.sup.j, C(O)NR.sup.iR.sup.j, N[C(O)R.sup.iC(O)R.sup.i], SR.sup.i, halogen, CN, SiR.sup.SivR.sup.SiwR.sup.Six and NO.sub.2: and one or two CH.sub.2-groups, but not adjacent CH.sub.2-groups, of C.sub.5-12-cycloalkyl are optionally replaced by O, S, OC(O), CO, NR.sup.i or NR.sup.iCO, wherein, in R.sup.31, R.sup.32, R.sup.41, and R.sup.42, C.sub.6-18-aryl and 5 to 20 membered heteroaryl are optionally substituted with one to six substituents independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 14 membered heteroaryl, OR.sup.i, OC(O)R.sup.j, C(O)OR.sup.i, C(O)R.sup.i, NR.sup.iR.sup.j, NR.sup.iC(O)R.sup.j, C(O)NR.sup.iR.sup.j, N[C(O)R.sup.i][C(O)R.sup.j], SR.sup.i, halogen, CN, SiR.sup.SivR.sup.SiwR.sup.Six and NO.sub.2, wherein R.sup.Siv, R.sup.Siw, and R.sup.Six are each independently selected from the group consisting of H, C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-6-cycloalkyl, phenyl and O-Si(CH.sub.3).sub.3, wherein R.sup.i, R.sup.jare each independently selected from the group consisting of H, C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, and 5 to 14 membered heteroaryl, wherein, in R.sup.Siv, R.sup.Siw, R.sup.Six, R.sup.i, R.sup.j, C.sub.1-20-alkyl, C.sub.2-20-alkenyl and C.sub.20-alkynyl are optionally substituted with one to five substituents selected from the group consisting of C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.k, OC(O)R.sup.1, C(O)OR.sup.k, C(O)R.sup.k, NR.sup.kR.sup.1, NR.sup.kC(O)R.sup.1, C(O)NR.sup.kR.sup.l, N[C(O)R.sup.k][C(O)R.sup.1], SR.sup.k, halogen, CN, and NO.sub.2, wherein, in R.sup.Siv, R.sup.Siw, R.sup.Six, R.sup.i, and R.sup.j, C.sub.5-8-cycloalkyl is optionally substituted with one to five substituents selected from the group consisting of C.sub.1-10-alkyl, C.sub.2-10-alkenyl, C.sub.2-10-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.k, OC(O)R.sup.l, C(O)OR.sup.k, C(O)R.sup.k, NR.sup.kR.sup.l, NR.sup.kC(O)R.sup.l, C(O)NR.sup.kR.sup.1, N[C(O)R.sup.k][C(O)R.sup.1], SR.sup.k, halogen, CN, and NO.sub.2. wherein, in R.sup.Siv, R.sup.Siw, R.sup.Six, R.sup.i, and R.sup.j, C.sub.6-14-aryl and 5 to 14 membered heteroaryl are optionally substituted with one to five substituents independently selected from the group consisting of C.sub.1-10-alkyl, C.sub.2-10-alkenyl, C.sub.2-10-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.k, OC(O)R.sup.1, C(O)OR.sup.k, C(O)R.sup.k, NR.sup.kR.sup.l, NR.sup.kC(O)R.sup.1, C(O)NR.sup.kR.sup.1, N[C(O)R.sup.k][C(O)R.sup.l], SR.sup.k, halogen, CN, and NO.sub.2, wherein R.sup.k and R.sup.l, are independently selected from the group consisting of H, C.sub.1-10-alkyl, C.sub.2-10-alkenyl and C.sub.2-10-alkynyl, and wherein, in R.sup.k and R.sup.l, C.sub.1-10-alkyl, C.sub.2-10-alkenyl and C.sub.2-10-alkynyl are optionally substituted with one to five substituents selected from the group consisting of halogen, CN and NO.sub.2.

2. The polymer of claim 1, wherein L.sup.1 and L.sup.2 are each independently selected from the group consisting of C.sub.6-30-arylene and 5 to 30 membered heteroarylene, and ##STR00087## wherein C.sub.6-30-arylene and 5 to 30 membered heteroarylene are optionally substituted with one to six substituents R.sup.3 selected from the group consisting of C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.5-12-cycloalkyl, C.sub.6-18-aryl and 5 to 20 membered heteroaryl, OR.sup.31, OC(O)R.sup.31, C(O)OR.sup.31, C(O)R.sup.31, NR.sup.31R.sup.32, NR.sup.31C(O)R.sup.32, C(O)NR.sup.31R.sup.32, SR.sup.31, halogen, CN, SiR.sup.SivR.sup.SiwR.sup.Sixand OH, and wherein ##STR00088## is optionally substituted with one or two substituents R.sup.4 selected from the group consisting of C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.5-12-cycloalkyl, C.sub.6-18-aryl and 5 to 20 membered heteroaryl, C(O)R.sup.41, C(O)NR.sup.41R.sup.42, C(O)OR.sup.41 and CN, wherein R.sup.31, R.sup.32, R.sup.41 and R.sup.42 are each independently selected from the group consisting of H, C.sub.1-30alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.5-12-cycloalkyl, C.sub.6-18-aryl and 5 to 20 membered heteroaryl, wherein, R.sup.31, R.sup.32, R.sup.41, and R.sup.42, C.sub.1-30-alkyl, C.sub.2-30-alkenyl and C.sub.2-30-alkynyl are optionally substituted with one to ten substituents independently selected from the group consisting of C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 14 membered heteroaryl, OR.sup.i, OC(O)R.sup.j, C(O)- OR.sup.i, C(O)R.sup.i, NR.sup.iR.sup.j, NR.sup.iC(O)R.sup.j, C(O)NR.sup.iR.sup.j, N[C(O)R.sup.i][C(O)R.sup.j], SR.sup.i, halogen, CN, SiR.sup.SivR.sup.SiwR.sup.Six and NO.sub.2; and at least two CH.sub.2-groups, but not adjacent CH.sub.2-groups of C.sub.1-30- alkyl, C.sub.2-30-alkenyl and C.sub.2-30-alkynyl are optionally replaced by O or S, wherein, R.sup.31, R.sup.32, R.sup.41, and R.sup.42, C.sub.5-12-cycloalkyl is optionally substituted with one to six substituents independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl and C.sub.2-20alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 14 membered heteroaryl, OR.sup.i, OC(O)R.sup.j, C(O)OR.sup.i, C(O)R.sup.i, NR.sup.iR.sup.j, NRC(O)R.sup.k, C(O)NR.sup.iR.sup.j, N[C(O)R.sup.i][C(O)R.sup.j], SR.sup.i, halogen, CN, SiR.sup.SivR.sup.SiwR.sup.Six and NO.sub.2; and one or two CH.sub.2-groups, but not adjacent CH.sub.2-groups, of C.sub.5-12-cycloalkyl are optionally replaced by O, S, OC(O), CO, NR.sup.ior NR.sup.iCO, wherein, R.sup.31, R.sup.32, R.sup.41, and R.sup.42, C.sub.6-18-aryl and 5 to 20 membered heteroaryl are optionally substituted with one to six substituents independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 14 membered heteroaryl, OR.sup.i, OC(O)R.sup.j, C(O)OR.sup.i, C(O)R.sup.i, NR.sup.iR.sup.j, NR.sup.iC(O)R.sup.j, C(O)NR.sup.iR.sup.j, N[C(O)R.sup.i][C(O)R.sup.j], SR.sup.i, halogen, CN, SiR.sup.SivR.sup.SiwR.sup.Six and NO.sub.2, wherein SiR.sup.SivR.sup.SiwR.sup.Six are each independently selected from the group consisting of H, C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-6-cycloalkyl, phenyl and O-Si(CH.sub.3).sub.3, and wherein R.sup.i and R.sup.j are independently selected from the group consisting of H, C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, and 5 to 14 membered heteroaryl, wherein, in R.sup.i and R.sup.j, C.sub.1-20-alkyl, C.sub.2-20-alkenyl and C.sup.2-20-alkynyl are optionally substituted with one to five substituents selected from the group consisting of C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.k, OC(O)R.sup.l, C(O)OR.sup.k, C(O)R.sup.k, NR.sup.kR.sup.1, NR.sup.kC(O)R.sup.1, C(O)NR.sup.kR.sup.1, N[C(O)R.sup.k][C(O)R.sup.1], SR.sup.k, halogen, CN, and NO.sub.2, wherein, in R.sup.i and R.sup.j , C.sub.5-8-cycloalkyl is optionally substituted with one to five substituents selected from the group consisting of C.sub.1-10-alkyl, C.sub.2-10-alkenyl, C.sub.2-10-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.k, OC(O)R.sup.1, C(O)OR.sup.k, C(O)R.sup.k, NR.sup.kR.sup.1, NR.sup.kC(O)R.sup.1, C(O)NR.sup.kR.sup.1, N[C(O)R.sup.k][C(O)R.sup.l], SR.sup.k, halogen, CN, and NO.sub.2, wherein, in R.sup.i and R.sup.j, C.sub.6-14-aryl and 5 to 14 membered heteroaryl are optionally substituted with one to five substituents independently selected from the group consisting of C.sub.1-10-alkyl, C.sub.2-10-alkenyl, C.sub.2-10-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.k, OC(O)R.sup.1, C(O)OR.sup.k, C(O)R.sup.k, NR.sup.kR.sup.1, NR.sup.kC(O)R.sup.1, C(O)NR.sup.kR.sup.1, N[C(O)R.sup.k][C(O)R.sup.1], SR.sup.k, halogen, CN, and NO.sub.2, wherein R.sup.k and R.sup.1 are independently selected from the group consisting of H, C.sub.1-10alkyl, C.sub.2-10-alkenyl and C.sub.2-10-alkynyl, and wherein, in R.sup.k and R.sup.1, C.sub.2-10-alkenyl and C.sub.2-10-alkynyl are optionally substituted with one to five substituents selected from the group consisting of halogen, CN and NO.sub.2.

3. The polymer of claim 2, wherein L.sup.1 and L.sup.2 are each independently selected from the group consisting of C.sub.6-30-arylene and 5 to 30 membered heteroarylene, and ##STR00089## wherein C.sub.6-30-arylene and 5 to 30 membered heteroarylene is selected from the group consisting of ##STR00090## ##STR00091## ##STR00092## wherein R.sup.l is selected from the group consisting of C.sub.1-36-alkyl, C.sub.3-36-alkenyl and C.sub.3-36alkynyl, wherein C.sub.1-36-alkyl, C.sub.3-36-alkenyl and C.sub.3-36-alkynyl are optionally substituted with one to twenty substituents independently selected from the group consisting of C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.a, SR.sup.a, Si(R.sup.sia)(R.sup.Sib)(R.sup.Sic), O-Si(R.sub.Sia)(R.sup.Sib)(R.sup.Sic), halogen, and CN; and at least two CH.sub.2-groups, but not adjacent CH.sub.2-groups, of C.sub.1-36-alkyl, C.sub.2-36-alkenyl and C.sub.2-36-alkynyl are optionally replaced by O or S, wherein R.sup.a is independently selected from the group consisting of H, C.sub.3-20-alkenyl, C.sub.3-20-alkynyl, C.sub.5-6-cycloalkyl and C.sub.6-10aryl, wherein R.sup.Sia, R.sup.Sib and R.sup.Sic are independently selected from the group consisting of H, C.sub.1-26-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, [O-SiR.sup.SidR.sup.Sie].sub.0R.sup.Sif wherein o is an integer from 1 to 50, wherein R.sup.Sid, R.sup.Sie, R.sup.Sif are independentl selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, -[O-SiR.sup.SigR.sup.Sih].sub.pR.sup.Sii, wherein p is an integer from 1 to 50, wherein R.sup.Sig R.sup.Sih, R.sup.Sii are indeendently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, O-Si(CH.sub.3).sub.3, C.sub.1-20-alkyl, C.sub.2-20-alkenyl and C.sub.2-20-alkynyl are optionally substituted with one to ten substituents selected from the group consisting of halogen and CN, wherein R.sup.104 and R.sup.105 are independently and at each occurrence selected from the group consisting of H, C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, and 5 to 14 membered heteroaryl, or R.sup.104 and R.sup.105, if attached to the same atom, together with the atom, to which they are attached, form a 5 to 12 membered ring system, wherein, in R.sup.104 and R.sup.105, C.sub.1-20-alkyl, C.sub.2-20-alkenyl and C.sub.2-20-alkynyl are optionally substituted with one to five substituents selected from the group consisting of C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.s, OC(O)R.sup.l, C(O)OR.sup.s, C(O)R.sup.s, NR.sup.sR.sup.t, NR.sup.sC(O)R.sup.1, C(O)NR.sup.sR.sup.t, N[C(O)R.sup.s][C(O)R.sup.t], SR.sup.s, halogen, CN, and NO.sub.2, wherein, in R.sup.104 and R.sup.105, C.sub.5-8-cycloalkyl is optionally substituted with one to five substituents selected from the group consisting of C.sub.1-10-alkyl, C.sub.2-10-alkenyl, C.sub.2-10-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.s, OC(O)R.sup.t, C(O)OR.sup.s, C(O)R.sup.s, NR.sup.sR.sup.t, NR.sup.sC(O)R.sup.t, C(O)NR.sup.sR.sup.t, N[C(O)R.sup.s][C(O)R.sup.l], SR.sup.s, halogen, CN, and NO.sub.2, wherein, in R.sup.104 and R.sup.105, C.sub.6-14-aryl and 5 to 14 membered heteroaryl are optionally substituted with one to five substituents independently selected from the group consisting of C.sub.1-10-alkyl, C.sub.2-10-alkenyl, C.sub.2-10-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.s, OC(O)R.sup.t, C(O)OR.sup.s, C(O)R.sup.s, NR.sup.sR.sup.t, NR.sup.sC(O)R.sup.t, C(O)NR.sup.sR.sup.t, N[C(O)R.sup.s][C(O)R.sup.t], SR.sup.s, halogen, CN, and NO.sub.2, wherein, in R.sup.104 and R.sup.105, 5 to 12 membered ring system is optionally substituted with one to five substituents selected from the group consisting of C.sub.1-10-alkyl, C.sub.2-10-alkenyl, C.sub.2-10-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.3, OC(O)R.sup.t, C(O)OR.sup.s, C(O)-R.sup.s, NR.sup.sR.sup.t, NR.sup.sC(O)R.sup.t, C(O)NR.sup.sR.sup.t, N[C(O)R.sup.s][C(O)R.sup.t], SR.sup.s, halogen, CN, and NO.sub.2, wherein R.sup.s and R.sup.t are independently selected from the group consisting of H, C.sub.1-10-alkyl, C.sub.2-10-alkenyl and C.sub.2-10-alkynyl, wherein, in R.sup.s and R.sup.t , C.sub.1-10-alkyl, C.sub.2-10-alkenyl and C.sub.2-10-alkynyl are optionally substituted with one to five substituents selected from the group consisting of halogen, CN and NO.sub.2, wherein C.sub.6-30-arylene and 5 to 30 membered heteroarylene are optionally substituted with one to six substituents R.sup.3 at each occurrence selected from the group consisting of C.sub.1-30-alkyl and halogen, wherein ##STR00093## is optionally substituted with one or two substituents R.sup.4 selected from the group consisting of C.sub.1-30-alkyl, C(O)R.sup.41, C(O)OR.sup.41 and CN, and wherein R.sup.41 is at each occurrence C.sub.1-30-alkyl.

4. The polymer of claim 3, wherein L.sup.1 and L.sup.2 are each independently selected from a group consisting of ##STR00094## ##STR00095## and wherein L.sup.1 and L.sup.2 are not further substituted.

5. The polymer of claim 1, wherein L.sup.1 and L.sup.2 are selected from ##STR00096##

6. The polymer of claim 1, wherein: n is 0, 1, or 2; and m is 0, 1, or 2.

7. An electronic device, comprising the polymer of claim 1.

8. The electronic device of claim 7, wherein the electronic device is an organic field effect transistor.

9. The polymer of claim 1, comprising at least 2 units of the formula 1 and having a M.sub.n of up to 15000 and/or M.sub.w of up to 26000.

10. The polymer of claim 1, wherein the polymer has a PDI up to 1.7.

11. A polymer comprising a unit of formula 1 ##STR00097## or a compound of formula 1: ##STR00098## wherein n is 1, 2, 3, or 4, m is 0, 1, 2, 3, or 4, R is hydrogen, C.sub.1-30-alkyl, and phenyl; wherein L.sub.1 comprises ##STR00099## wherein L.sub.2, is selected from the group consisting of C.sub.6-30-arylene, 5 to 30 membered heteroarylene, ##STR00100## wherein C.sub.6-30-arylene and 5 to 30 membered heteroarylene are optionally substituted with one to six substituents R.sup.3 selected from the group consisting of C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.5-12-cycloalkyl, C.sub.6-18-aryl, 5 to 20 membered heteroaryl, OR.sup.31, OC(O)R.sup.31, C(O)OR.sup.31, C(O)R.sup.31, NR.sup.31R.sup.32, NR.sup.31C(O)R.sup.32, C(O)NR.sup.31R.sup.32, N[C(O)R.sup.31][C(O)R.sup.32], SR.sup.31, halogen, CN, SiR.sup.SivR.sup.SiwR.sup.Six, and OH, wherein ##STR00101## are optionally substituted with one or two substituents R.sup.4 selected from the group consisting of C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.5-12-cycloalkyl, C.sub.6-18-aryl, 5 to 20 membered heteroaryl, C(O)R.sup.41, C(O)NR.sup.41R.sup.42, C(O)OR.sup.41, and CN, wherein R.sup.31, R.sup.32, R.sup.41, and R.sup.42 are each independently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.5-12-cycloalkyl, C.sub.6-18-aryl, and 5 to 20 membered heteroaryl, wherein, in R.sup.31, R.sup.32, R.sup.41, and R.sup.42, C.sub.1-30-alkyl, C.sub.2-30-alkenyl and C.sub.2-30-alkynyl are optionally substituted with one to ten substituents independently selected from the group consisting of C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 14 membered heteroaryl, OR.sup.i, OC(O)R.sup.j, C(O)OR.sup.IC(O)R.sup.i, NR.sup.iR.sup.I, NR.sup.iC(O)R.sup.j, C(O)NR.sup.iR.sup.j, N[C(O)R.sup.i][C(O)R.sup.j], SR.sup.i, halogen, CN, SiR.sup.SivR.sup.SiwR.sup.six, and NO.sub.2; and at least two CH.sub.2-groups, but not adjacent CH.sub.2-groups of C.sub.1-30-alkyl, C.sub.2-30-alkenyl and C.sub.2-30-alkynyl are optionally replaced by O or S, wherein, in R.sup.31, R.sup.32, R.sup.41, and R.sup.42, C.sub.5-12-cycloalkyl is optionally substituted with one to six substituents independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl and C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 14 membered heteroaryl, OR.sup.i, OC(O)R.sup.j, C(O)OR.sup.i, C(O)R.sup.i, NR.sup.iR.sup.j, NR.sup.iC(O)R.sup.j, C(O)NR.sup.iR.sup.j, N[C(O)R.sup.i][C(O)R.sup.j], SR.sup.i, halogen, CN, SiR.sup.SivR.sup.SiwR.sup.Six, and NO.sub.2; and one or two CH.sub.2-groups, but not adjacent CH.sub.2-groups, of C.sub.5-12-cycloalkyl are optionally replaced by O, S, OC(O), CO, NR.sup.i, or NR.sup.i CO, wherein, in R.sup.31, R.sup.32, R.sup.41, and R.sup.42, C.sub.6-18-aryl and 5 to 20 membered heteroaryl are optionally substituted with one to six substituents independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 14 membered heteroaryl, OR.sup.i, OC(O)R.sup.j, C(O)OR.sup.i, C(O)R.sup.i, NR.sup.iR.sup.j, NR.sup.iC(O)R.sup.j, C(O)NR.sup.iR.sup.j, N[C(O)R.sup.I][C(O)R.sup.j], SR.sup.i, halogen, CN, SiR.sup.SivR.sup.SiwR.sup.Six, and NO.sub.2, wherein R.sup.Siv, R.sup.Siw, R.sup.Six are each independently selected from the group consisting of H, C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-6-cycloalkyl, phenyl and O-Si(CH.sub.3).sub.3, wherein R.sup.i and R.sup.j are independently selected from the group consisting of H, C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, and 5 to 14 membered heteroaryl, wherein, in R.sup.Siv, R.sup.Siw, R.sup.Six, R.sup.i, R.sup.j, C.sub.1-20-alkyl, C.sup.2-20-alkenyl, and C.sub.2-20-alkynyl are optionally substituted with one to five substituents selected from the group consisting of C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.k, OC(O)R.sup.1, C(O)OR.sup.k, C(O)R.sup.k, NR.sup.kR.sup.1, NR.sup.kC(O)R.sup.1, C(O)NR.sup.kR.sup.1, N[C(O)R.sup.k][C(O)R.sup.1], SR.sup.k, halogen, CN, and NO.sub.2, wherein, in R.sup.Siv, R.sup.Siw, R.sup.Six, R.sup.i, and R.sup.j, C.sub.5-8-cycloalkyl is optionally substituted with one to five substituents selected from the group consisting of C.sub.1-10-alkyl, C.sub.2-10-alkenyl, C.sub.2-10-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.k, OC(O)R.sup.1, C(O)OR.sup.k, C(O)R.sup.k, NR.sup.kR.sup.1, NR.sup.kC(O)R.sup.1, C(O)NR.sup.kR.sup.1, N[C(O)R.sup.k][C(O)R.sup.1], SR.sup.k, halogen, CN, and NO.sub.2, wherein, in R.sup.Siv, R.sup.Siw, R.sup.Six, R.sup.i, R.sup.j, C.sub.6-14-aryl and 5 to 14 membered heteroaryl are optionally substituted with one to five substituents independently selected from the group consisting of C.sub.1-10-alkyl, C.sub.2-10-alkenyl, C.sub.2-10-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.k, OC(O)R.sup.1, C(O)OR.sup.k, C(O)R.sup.k, NR.sup.kR.sup.1, NR.sup.kC(O)R.sup.1, C(O)NR.sup.kR.sup.l, N[C(O)R.sup.k][C(O)R.sup.1], SR.sup.k, halogen, CN, and NO.sub.2, wherein R.sup.k and R.sup.1 are independently selected from the group consisting of H, C.sub.1-10-alkyl, C.sub.2-10-alkenyl, and C.sub.2-10-alkynyl, and wherein, in R.sup.k and R.sup.1, C.sub.1-10-alkyl, C.sub.2-10-alkenyl, and C.sub.2-10-alkynyl are optionally substituted with one to five substituents selected from the group consisting of halogen, CN, and NO.sub.2.

12. The polymer or compound of claim 11, wherein L.sup.2 is selected from the group consisting of C.sub.6-30-arylene and 5 to 30 membered heteroarylene, and ##STR00102## wherein C.sub.6-30-arylene and 5 to 30 membered heteroarylene are optionally substituted with one to six substituents R.sup.3 selected from the group consisting of C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.5-12-cycloalkyl, C.sub.6-18-aryl, 5 to 20 membered heteroaryl, OR.sup.31, OC(O)R.sup.31, C(O)OR.sup.31, C(O)-R.sup.31, NR.sup.31R.sup.32, NR.sup.31C(O)R.sup.32, C(O)NR.sup.31R.sup.32, SR.sup.31, halogen, CN, SiR.sup.SivR.sup.SiwR.sup.Six, and OH, and wherein ##STR00103## is optionally substituted with one or two substituents R.sup.4 selected from the group consisting of C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.5-12-cycloalkyl, C.sub.6-18-aryl and 5 to 20 membered heteroaryl, C(O)R.sup.-41, C(O)NR.sup.41R.sup.42, C(O)OR.sup.41, and CN, wherein R.sup.31, R.sup.32, R.sup.41, and R.sup.42 are each independently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.5-12-cycloalkyl, C.sub.6-18-aryl, and 5 to 20 membered heteroaryl, wherein, R.sup.31, R.sup.32, R.sup.41, and R.sup.42, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, and C.sub.2-30-alkynyl are optionally substituted with one to ten substituents independently selected from the group consisting of C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 14 membered heteroaryl, OR.sup.i, OC(O)R.sup.j, C(O)OR.sup.i, C(O)-R.sup.i, NR.sup.iR.sup.j, NR.sup.iC(O)R.sup.j, C(O)NR.sup.iR.sup.j, N[C(O)R.sup.i][C(O)R.sup.j], SR.sup.i, halogen, CN, SiR.sup.SivR.sup.SiwR.sup.Six, and NO.sub.2; and at least two CH.sub.2-groups, but not adjacent CH.sub.2-groups of C.sub.1-30-alkyl, C.sub.2-30-alkenyl, and C.sub.2-30-alkynyl are optionally replaced by O or S, wherein, R.sup.31, R.sup.32, R.sup.41, and R.sup.42, C.sub.5-12-cycloalkyl is optionally substituted with one to six substituents independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl and C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 14 membered heteroaryl, OR.sup.i, OC(O)R.sup.j, C(O)OR.sup.i, C(O)R.sup.i, NR.sup.iR.sup.j, NR.sup.iC(O)R.sup.j, C(O)NR.sup.iR.sup.j, N[C(O)R.sup.i], [C(O)R.sup.j], SR.sup.i, halogen, CN, SiR.sup.SivR.sup.SiwR.sup.Six, and NO.sub.2; and one or two CH.sub.2-groups, but not adjacent CH.sub.2-groups, of C.sub.5-12-cycloalkyl are optionally replaced by O, S, OC(O), CO, NR.sup.i, or NR.sup.iCO, wherein, R.sup.31, R.sup.32, R.sup.41, and R.sup.42, C.sub.6-18-aryl and 5 to 20 membered heteroaryl are optionally substituted with one to six substituents independently selected from the group consisting of C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, 5 to 14 membered heteroaryl, OR.sup.i, OC(O)R.sup.j, C(O)OR.sup.i, C(O)R.sup.i, NR.sup.iR.sup.j, NR.sup.iC(O)R.sup.j, C(O)NR.sup.iR.sup.j, N[C(O)R.sup.i][C(O)R.sup.j], SR.sup.i, halogen, CN, SiRs.sup.SivR.sup.SiwR.sup.Six, and NO.sub.2, wherein SiR.sup.SivR.sup.SiwR.sup.Sixare each independently selected from the group consisting of H, C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-6-cycloalkyl, phenyl, and O-Si(CH.sub.3).sub.3, and wherein R.sup.iand R.sup.jare independently selected from the group consisting of H, C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, and 5 to 14 membered heteroaryl, wherein, in R.sup.iand R.sup.j, C.sub.1-20-alkyl, C.sub.2-20-alkenyl and C.sub.2-20-alkynyl are optionally substituted with one to five substituents selected from the group consisting of C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.k, OC(O)R.sup.1, C(O)OR.sup.k, C(O)R.sup.k, NR.sup.kR.sup.l, NR.sup.kC(O)R.sup.1, C(O)NR.sup.kR.sup.1, N[C(O)R.sup.k][C(O)R.sup.1], SR.sup.k, halogen, CN, and NO.sub.2, wherein, in R.sup.i and R.sup.j, C.sub.5-8-cycloalkyl is optionally substituted with one to five substituents selected from the group consisting of C.sub.1-10-alkyl, C.sub.2-10-alkenyl, C.sub.2-10alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.k, OC(O)R.sup.1, C(O)OR.sup.k, C(O)R.sup.k, NR.sup.kR.sup.1, NR.sup.kC(O)R.sup.1, C(O)NR.sup.kR.sup.1, N [C(O)R.sup.k][C(O)R.sup.1], SR.sup.k, halogen, CN, and NO.sub.2, wherein, in R.sup.i and R.sup.j, C.sub.6-14-aryl, and 5 to 14 membered heteroaryl are optionally substituted with one to five substituents independently selected from the group consisting of C.sub.1-10-alkyl, C.sub.2-10-alkenyl, C.sub.2-10-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.k, OC(O)R.sup.1, C(O)OR.sup.k, C(O)R.sup.k, NR.sup.kR.sup.1, NR.sup.kC(O)R.sup.1, C(O)NR.sup.kR.sup.1, N[C(O)R.sup.k][C(O)R.sup.1], SR.sup.k, halogen, CN, and NO.sub.2, wherein R.sup.k and R.sup.1 are independently selected from the group consisting of H, C.sub.1-10-alkyl, C.sub.2-10-alkenyl, and C.sub.2-10-alkynyl, and wherein, in R.sup.k and R.sup.1, C.sub.1-10-alkyl, C.sub.2-10-alkenyl, and C.sub.2-10-alkynyl are optionally substituted with one to five substituents selected from the group consisting of halogen, CN and NO.sub.2.

13. The polymer or compound of claim 12, wherein L.sup.2 is selected from the group consisting of C.sub.6-30-arylene and 5 to 30 membered heteroarylene, and ##STR00104## wherein C.sub.6-30-arylene and 5 to 30 membered heteroarylene is selected from the group consisting of ##STR00105## ##STR00106## ##STR00107## wherein R.sup.1 is selected from the group consisting of C.sub.1-36-alkyl, C.sub.3-36-alkenyl, and C.sub.3-36-alkynyl, wherein C.sub.1-36-alkyl, C.sub.3-36-alkenyl and C.sub.3-36-alkynyl are optionally substituted with one to twenty substituents independently selected from the group consisting of C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.a, SR.sup.a, Si(R.sup.Sia)(R.sup.Sib)(R.sup.Sic), OSi(R.sup.Sia)(R.sup.Sib)(R.sup.Sic), halogen, and CN; and at least two CH.sub.2-groups, but not adjacent CH.sub.2,-groups, of C.sub.1-36-alkyl, C.sub.2-36-alkenyl, and C.sub.2-36-alkynyl are optionally replaced by O or S, wherein R.sup.a is independently selected from the group consisting of H, C.sub.3-20-alkenyl, C.sub.3-20-alkynyl, C.sub.5-6-cycloalkyl, and C.sub.6-10-aryl, wherein R.sup.Soa, R.sup.Sib and R.sup.Sic are independently selected from the group consisting of H, C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, and -[O-SiR.sup.SidR.sup.Sie].sub.oR.sup.Sif wherein o is an integer from 1 to 50, wherein R.sup.Sid, R.sup.Sie, R.sup.Sif are independently selected from the group consisting of H, C.sub.1-30- alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, and [O-SiR.sup.SigR.sup.Sih]pR.sup.Sii, wherein p is an integer from 1 to 50, wherein R.sup.Sig R.sup.Sih, R.sup.Sii are independently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, and O-Si(CH.sub.3).sub.3, C.sub.1-20-alkyl, C.sub.2-20-alkenyl, and C.sub.2-20-alkynyl are optionally substituted with one to ten substituents selected from the group consisting of halogen and CN, wherein R.sup.104 and R.sup.105 are independently and at each occurrence selected from the group consisting of H, C.sub.1-20-alkyl, C.sub.2-20-alkenyl, C.sub.2-20-alkynyl, C.sub.5-8-cycloalkyl, C.sub.6-14-aryl, and 5 to 14 membered heteroaryl, or R.sup.104 and R.sup.105, if attached to the same atom, together with the atom, to which they are attached, form a 5 to 12 membered ring system, wherein, in R.sup.104 and R.sup.105, C.sub.1-20-alkyl, C.sub.2-20-alkenyl, and C.sub.2-20-alkynyl are optionally substituted with one to five substituents selected from the group consisting of C.sub.5-6-cycloalkyl, C.sub.6-l0-aryl, 5 to 10 membered heteroaryl, OR.sup.s, OC(O)R.sup.t, C(O)OR.sup.s, C(O)R.sup.s, NR.sup.sR.sup.t, NR.sup.sC(O)R.sup.t, C(O)NR.sup.sR.sup.t, N[C(O)R.sup.s][C(O)R.sup.t], SR.sup.s, halogen, CN, and NO.sub.2, wherein, in R.sup.104 and R.sup.105, C.sub.5-8-cycloalkyl is optionally substituted with one to five substituents selected from the group consisting of C.sub.1-10-alkyl, C.sub.2-10-alkenyl, C.sub.2-10-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.s, OC(O)R.sup.t, C(O)OR.sup.s, C(O)R.sup.s, NR.sup.sR.sup.t, NR.sup.sC(O)R.sup.t, C(O)NR.sup.sR.sup.t, N[C(O)R.sup.s][C(O)R.sup.t], SR.sup.s, halogen, CN, and NO.sub.2, wherein, in R.sup.104 and R.sup.105, C.sub.6-14-aryl and 5 to 14 membered heteroaryl are optionally substituted with one to five substituents independently selected from the group consisting of C.sub.1-10-alkyl, C.sub.2-10-alkenyl, C.sub.2-10-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.s, OC(O)R.sup.t, C(O)OR.sup.s, C(O)R.sup.s, NR.sup.sR.sup.t, NR.sup.sC(O)R.sup.t, C(O)NR.sup.sR.sup.t, N[C(O)R.sup.s][C(O)R.sup.t], SR.sup.s, halogen, CN, and NO.sub.2, wherein, in R.sup.104 and R.sup.105, 5 to 12 membered ring system is optionally substituted with one to five substituents selected from the group consisting of C.sub.1-10-alkyl, C.sub.2-10-alkenyl, C.sub.2-10-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, 5 to 10 membered heteroaryl, OR.sup.s, OC(O)R.sup.t, C(O)OR.sup.s, C(O)R.sup.s, NR.sup.sR.sup.t, NR.sup.sC(O)R.sup.t, C(O)NR.sup.sR.sup.t, N[C(O)R.sup.s][C(O)R.sup.t], SR.sup.s, halogen, CN, and NO.sub.2, wherein R.sup.s and R.sup.t are independently selected from the group consisting of H, C.sub.1-10- alkyl, C.sub.2-10-alkenyl, and C.sub.2-10-alkynyl, wherein, in R.sup.s and R.sup.t, C.sub.1-10-alkyl, C.sub.2-10-alkenyl and C.sub.2-10-alkynyl are optionally substituted with one to five substituents selected from the group consisting of halogen, CN, and NO.sub.2, wherein C.sub.6-30-arylene and 5 to 30 membered heteroarylene are optionally substituted with one to six substituents R.sup.3 at each occurrence selected from the group consisting of C.sub.1-30-alkyl and halogen, wherein ##STR00108## is optionally substituted with one or two substituents R.sup.4 selected from the group consisting of C.sub.1-30-alkyl, C(O)R.sup.41, C(O)OR.sup.41 and CN, and wherein R.sup.41is at each occurrence C.sub.1-30-alkyl.

14. The polymer or compound of claim 13, wherein L.sup.2 is selected from a group consisting of ##STR00109## ##STR00110## wherein L.sup.1 and L.sup.2 are not further substituted.

15. The polymer or compound of claim 11, wherein L.sup.2 is selected from ##STR00111##

16. The polymer or compound of claim 11, wherein: n is 1, or 2; and m is 0, 1, or 2.

17. An electronic device, comprising the polymer or compound of claim 11.

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

19. The polymer or compound of claim 11, wherein L.sub.1 comprises: ##STR00112##

20. The polymer or compound of claim 11, wherein L.sub.1 comprises: ##STR00113##

Description

EXAMPLES

Example 1

Naphthalene-2,6-diyl bis(diethylcarbamate)

(1) ##STR00072##

(2) 10 g (62.4 mmol) of napththalene 2,6-diol were dissolved in 100 ml of THF and added to a stirred suspension of NaH (50% in mineral oil, 9 g, 187.3 mmol, 3 equiv) in THF (80 ml) at 0 C. Then, the resulting suspension was stirred at 0 C. for one hour before 23.7 ml of diethylcarbamoyl chloride (187.3 mmol, 3 equiv.) were added dropwise. The reaction was allowed to warm up to room temperature and stirred overnight. Then, the reaction was carefully quenched by adding a few drops of water. Then, the THF was removed by distillation and the residue was extracted with H.sub.2O and ethyl acetate. The organic layer was washed with aq. KOH (1M) and H.sub.2O, then dried over MgSO.sub.4 and evaporated. The retrieved product could be used without further purification Yield 22.2 g (99%)

(3) .sup.1H NMR (400 MHz, CDCl.sub.3, ) 7.77 (d, 2H), 7.57 (dd, 2H), 7.28 (dd, 2H), 3.45 (m, 8H), 1.25 (m, 12H)

(4) .sup.13C-NMR (100 MHz, CDCl.sub.3, ) 13.29, 14.16, 41.82, 42.16, 118.19, 122.08, 128.51, 131.37, 148.74, 154.20

Example 2

N2,N2,N6,N6-tetraethyl-3,7-dihydroxynaphthalene-2,6-dicarboxamide

(5) ##STR00073##

(6) Under an argon atmosphere, 162 mL of LDA solution (323.6 mmol, 2M in THF/heptane/ethylbenzene, 5 equiv.) were slowly added via a syringe to a solution of 23.2 g (64.7 mmol, 1.0 equiv) of naphthalene-2,6-diyl bis(diethylcarbamate) in THF (600 ml) at 78 C. The resulting mixture was allowed to warm to room temperature overnight while it turned deep green. Then, the reaction mixture was carefully quenched with HCl(2M) solution, and the formed precipitate was filtered off and washed with Et.sub.2O. After drying, 11.29 g (49%) of a pale yellow solid were obtained which could be used without further purification.

(7) .sup.1H NMR (400 MHz, DMSO-d.sup.6, ): 9.72 (s, 2H), 7.46, (s, 2H), 7.12 (s, 2H), 3.45 (m, 4H), 3.13 (m, 4H), 1.16 (t, 6H), 1.00 (t, 6H)

(8) .sup.13C-NMR (100 MHz, DMSO-d.sup.6, ): 167.6, 149.4, 129.0, 128.1, 124.4, 109.3, 44.2, 42.3, 13.9, 12.9

(9) ESI-TOF-MS: for C.sub.20H.sub.27N.sub.2O.sub.4 [M+] calc'd 359.1971 found 359.1989

Example 3

3,7-Bis((tert-butyldimethylsilyl)oxy)-N.SUP.2., N.SUP.2., N.SUP.6., N.SUP.6.-tetraethylnaphthalene-2,6-dicarboxamide

(10) 10.54 g N.sup.2,N.sup.200-tetraethyl-3,7-dihydroxynaphthalene-2,6-dicarboxamide were dissolved in 50 ml of DMF and 8 g of imidazole were added. Then, TBSCI was added portionwise and the reaction mixture stirred at room temperature for 24 h. The reaction was quenched by pouring into water and the resulting white precipitate was filtered off, washed with copious amounts of water, and dried in vacuo Yield 16.85 g (98%).

(11) .sup.1H NMR (400 MHz, CDCl.sub.3, ): 7.54 (d, 2H), 7.07 (d, 2H), 3.57 (m, 2H), 3.19 (m, 2H), 1.27 (t, 3H), 1.03 (m, 3H), 0.98 (s, 18H), 0.20-0.28 (4s, 12H)

(12) .sup.13C-NMR (100 MHz, CDCl.sub.3, ): 168.8, 148.5, 132.4, 129.8, 125.9, 125.7, 114.7, 114.3, 43.2, 43.1, 39.5, 25.9, 18.4, 14.3, 13.5, -3.85, -3.9, -4.3, -4.4

Example 4

Dimethyl 3,7-dihydroxynaphthalene-2,6-dicarboxylate

(13) ##STR00074##

(14) 3,7-bis((tert-butyldimethylsilypoxy)-N.sup.2,N.sup.2,N.sup.6,N.sup.6-tetraethylnaphthalene-2,6-dicarboxamide (16.85 g, 28.7 mmol) was dissolved in anhydrous DCM and (CH.sub.3).sub.3OBF.sub.4 (10.19 g, 68.9 mmol, 2.4 equiv) was added in portions. After consumption of the amide was complete, as indicated by TLC (ca. 18 h), the reaction mixture was evaporated to dryness and methanol (100 ml) was added followed by a saturated solution of Na.sub.2CO.sub.3 (100 mL) and solid Na.sub.2CO.sub.3 (1 g). The resulting mixture was filtered and acidified with HCl to a pH of 1. The formed solid was recovered by filtration as a first fraction, which could be used without further purification (2.7 g, 34%). The organic layer was dried, evaporated and purified by silica gel filtration (chloroform as eluent) to yield a second fraction (1.2 g). 49% yield were obtained in total.

(15) .sup.1H NMR (400 MHz, CDCl.sub.3, ): 10.23 (s, 2H), 8.36 (s, 2H), 7.32 (s, 2H), 4.04 (s, 6H)

(16) .sup.13C-NMR (100 MHz, CDCl.sub.3, ): only sparingly soluble in chloroform: 130.6 (CH, arom, naptht), 112.7 (CH, arom, naptht), 52.8 (CH.sub.3)

Example 5

3,7-Bis(((trifluoromethyl)sulfonyl)oxy)naphthalene-2,6-dicarboxylic acid dimethylester

(17) ##STR00075##

(18) 1.58 g (5.7 mmol) of dimethyl 3,7-dihydroxynaphthalene-2,6-dicarboxylate were dissolved (suspended) in DCM (50 ml) and 2.5 ml dry pyridine were added. Then, the reaction mixture was cooled to 0 C. and 2.10 ml (3.514 g, 12.5 mmol, 2.2 equiv.) of triflic anhydride were added dropwise. The reaction mixture was allowed to warm up to room temperature and was stirred overnight. Then, water (20 ml) and 2M HCl (20 ml) were added and the aqueous phase was subsequently extracted with 250 mL DCM. The combined organic layers were extracted with sat. NaHCO3 solution (50 ml) and brine, dried over MgSO.sub.4 and evaporated to dryness. A white solid was retrieved which could be directly used for the next step. Yield: 2.63g (85%)

(19) .sup.1H NMR (400 MHz, CDCl.sub.3, ): 8.71 (s, 2H), 7.92 (s, 2H), 4.05 (s, 6H)

(20) .sup.13C-NMR (100 MHz, CDCl.sub.3, ): C 163.65, 146.31, 134.49, 133.19, 126.06, 122.53, 120.57, 53.42

Example 6

3,7-Di(thiophen-2-yl)naphthalene-2,6-dicarboxylic Acid Dimethylester

(21) ##STR00076##

(22) A mixture of 3,7-bis(((trifluoromethyl)sulfonyl)oxy)naphthalene-2,6-dicarboxylic acid dimethyl-ester (2.59 g, 4.79 mmol), 2-thienylzinc bromide (0.50 M in THF, 24 ml, 12.16 mmol) and Pd(PPh.sub.3).sub.4 (265 mg, 0.243 mmol) was heated to reflux for 3 h. The reaction was allowed to cool to room temperature and sat. NH.sub.4Cl solution was added, after which a white precipitate formed. The product was recovered by filtration, washed with water and methanol and dried in vacuo to give dimethyl 3,7-di(thiophen-2-yl)naphthalene-2,6-dicarboxylic acid dimethyl ester as a pale yellow solid (1.62 g, 82%).

(23) .sup.1H NMR (400 MHz, CDCl.sub.3, ): 8.26 (s, 2H), 8.01 (s, 2H), 7.40 (dd, 2H), 7.12 (m, 4H), 3.81 (s, 6H).

(24) A .sup.13C-NMR could not be recorded due to poor solubility in chloroform.

Example 7

3,7-Di(thiophen-2-yl)naphthalene-2,6-dicarboxylic Acid

(25) ##STR00077##

(26) To a solution of 3,7-di(thiophen-2-yl)naphthalene-2,6-dicarboxylic acid dimethylester (1.28 g, 3.13 mmol) in ethanol (50 ml), a solution of sodium hydroxide (2.0 g NaOH in 15 ml water) was added. The reaction mixture was heated to reflux for 15 h. Then, the ethanol was removed on a rotary evaporator. The remaining aqueous solution was then acidified with concentrated hydro-chloric acid. The precipitated product was isolated by filtration, washed with water and methanol and dried in vacuo. 1.1 g (92%) of a yellow solid were obtained which could be used without further purification.

(27) .sup.1H NMR (400 MHz, DMSO-d.sup.6): (ppm) 13.24 (2H, COOH), 8.32 (s, 2H), 8.17 (s, 2H), 7.62 (dd, 2H), 7.21 (dd, 2H), 7.13 (dd, 2H)

(28) .sup.13C NMR (100 MHz, DMSO-d.sup.6): (ppm) 169.5, 141.1, 133.2, 131.7, 130.4, 129.6, 128.6, 127.8, 126.9, 126.7

Example 8

4,10-Dihydro-naphtho[3,2:3,4;7,6:3,4] dicyclopenta[2,1-b:2,1-b] dithiophene-4,10-dione

(29) ##STR00078##

(30) To a suspension of 3,7-di(thiophen-2-yl)naphthalene-2,6-dicarboxylic acid (1.1 g, 2.89 mmol) in anhydrous DCM (50 ml), oxalyl chloride (1.48 g g, 11.56 mmol) was added, followed by drop-wise addition of anhydrous DMF (200 l). The resultant mixture was stirred overnight at room temperature. Then, the solvents were removed in vacuo and after drying, the formed crude acid chloride (yellow solid) was redissolved in anhydrous DCM (80 ml). This solution was then added dropwise (via cannula) to a suspension of anhydrous AlCl.sub.3 (2 g) in DCM (50 ml) which was cooled to 0 C. The reaction mixture was stirred overnight while being allowed to warm up to room temperature. Then, it was poured onto ice containing HCl. A red precipitate was formed which was collected by filtration and washed with 2M HCl solution, water and acetone. After drying in vacuo, a red solid was obtained (748 mg, 75%).

(31) .sup.1H NMR (400 MHz, CDCl.sub.3, ): 7.83 (s, 2H) 7.49 (s, 2H), 7.29 (d, 2H), 7.21 (d, 2H)

(32) A .sup.130 spectrum could not be recorded due to poor solubility.

Example 9

4,10-Bis(hexadecylidene)-4,10-dihydro-naphtho[3,2:3,4;7,6:3,4] dicyclopenta[2,1-b:2,1-b]dithiophene

(33) ##STR00079##

(34) 2.712 g (4.78 mmol, 2.2 equiv.) of hexadecylphosphonium tribromide were dissolved in 60 ml of THF and cooled to 78 C. Then, 3 ml (4.78, 2.2 equiv.) of n-BuLi were added dropwise with a syringe and the resulting solution was stirred for 30 min at 78 C. Then 748 mg of 4,10-dihydro-naphtho[3,2:3,4;7,6:3,4] dicyclopenta[2,1-b:2,1-1] dithiophene-4,10-dione (2.17 mmol, 1 equiv) were suspended in 100 ml of THF and added dropwise via cannula.

(35) The reaction was left at 78 C. for 1 h and then let warm up to room temperature and carefully quenched by addition of water. The aqueous phase was extracted with 240 ml of EtOAc, dried over MgSO4 and dried in vacuo.

(36) The residue was purified by column chromatography (PET/EtAc 20/1) and 788 mg (48% yield) of a yellow solid were obtained which contained a mixture of three diastereomers. MALDI-TOF-MS: C.sub.52H.sub.72S.sub.2 [C.sub.52H.sub.73S.sub.2+=MH+] calc'd 761.52 found 760.7

Example 10

4,4,10,10-Tetrakis-(hexadecyl)-4,10-dihydro-naphtho[3,2:3,4;7,6:3,4]-dicyclopenta[2,1-b:2,1-b]-dithiophene

(37) ##STR00080##

(38) A 250 mL flask was charged with LiAlH.sub.4 (78.55 mg, 2.07 mmol), hexadecyl bromide (632 mg, 2.07 mmol), and 60 mL of dry THF. The solution was stirred and cooled down in an ice/water bath to approx. 15 C. before a solution of 4,10 bis(hexadecylidene)-4,10-dihydro-naphtho[3,2:3,4;7,6:3,4] dicyclopenta[2,1-b:2,1-b] dithiophene (788 mg, 1.04 mmol) in 60 mL of dry THF was added slowly via a syringe. More LiAIH.sub.4 (30 mg) and hexadecyl bromide (200 l) were added until the starting material was entirely consumed, then left to stir at RT for another hour. Then the reaction mixture was quenched by carefully adding H.sub.2O and the THF was distilled off. The residue was extracted with ethyl acetate and the combined organic layers dried over MgSO4. The crude was purified by column chromatography (using hexanes as eluent) followed by recrystallization from hexanes. Yield: 194 mg (15%).

(39) .sup.1H NMR (400 MHz, CDCl.sub.3, ): 7.76 (s, 2H), 7.64 (s, 2H), 7.33 (d, 2H), 6.99 (d, 2H), 1.95 (m, 8H) 1.3-1.15 (m, 112 H) 0.87 (t, 12H)

(40) MALDI-TOF-MS: C.sub.84H.sub.140S.sub.2 [C.sub.84H.sub.141S.sub.2+=MH+] calc'd 1214.1 found: 1214.2

Example 11

2,8-Dibromo-4,4,10,10-tetrakis-(hexadecyl)-4,10-dihydro-naphtho[3,2:3,4;7,6:3,4]-dicyclopenta[2,1-b:2,1-b]-dithiophene

(41) ##STR00081##

(42) A solution of 4,4,10,10-tetrakis-(hexadecyl)-4,10-dihydro-naphtho[3,2:3,4;7,6:3,4] dicyclopenta[2,1-b:2,1-b]-dithiophene (104 mg, 0.086 mmol) in chloroform (20 ml) was cooled to 0 C. under argon in the absence of light. N-bromosuccinimide (33.6 mg, 0.189 mmol) dissolved in chloroform (5 ml) was added in portions and the reaction progress was monitored by TLC. After full conversion had been detected, the reaction mixture was extracted with water, dried over magnesium sulphate and evaporated to dryness. The crude was purified by column chromatography (using hexanes as mobile phase) Yield: 107 mg of a white solid (90%).

(43) .sup.1H NMR (400 MHz, CDCl.sub.3, ): 7.69 (s, 2H), 7.62 (s, 2H), 7.00 (s, 2H), 1.92 (m, 8 H), 1.30-1.05 (m, 112 H), 0.87 (t, 12 H)

(44) .sup.13C-NMR (100 MHz, CDCl.sub.3, ): 155.35, 150.93, 141.57, 131.98, 125.03, 121.27, 116.66, 114.38, 54.64, 40.00, 32.15, 30.27, 29.90, 29.85, 29.59, 24.47, 22.92, 14.34

(45) MALDI-TOF-MS: C.sub.84H.sub.138Br.sub.2S.sub.2 [C.sub.84H.sub.139Br.sub.2S.sub.2+=MH+] calc'd 1371.9, found 1372.0

Example 12

(46) ##STR00082##

(47) 2,8-Dibromo-4,4,10,10-tetrakis(hexadecyl)-4,10-dihydro-naphtho[3,2:3,4;7,6:3,4] dicyclopenta[2,1-b:2,1-b]-dithiophene (85.63 mg, 0.06241 mmol) and 4,7-bis(4,4,5,5- tetramethyl-1,3,2-dioxaborolan-2-Abenzo[c][1,2,5]thiadiazole (24.23 mg, 0.06243 mmol) were placed in a 20 mL microwave vial. Pd.sub.2(dba).sub.3 (3.01 mg, 3.310.sup.3 mmol), (o-tol).sub.3P (4.03 mg, 0.0132 mmol), Aliquat 336 (1 drop) and toluene (5 ml) were added. This solution was degassed with argon for 30 min. Then, degassed Na.sub.2CO.sub.3 solution (1M) was added and the resulting mixture was degassed for another 10 minutes. Then, the vial was sealed and heated at 120 C. for 48 h.

(48) To end-cap the polymer chains, a few drops of bromobenzene were added (approx. 100 l) via a syringe and the reaction mixture was continued to reflux for 2 h. Then, phenylboronic acid (100 mg) was added and the reaction mixture was refluxed overnight. The resulting blue solution was precipitated into methanol and the precipitated polymer was recovered by filtration directly into an extraction thimble. Soxleth extractions were performed with acetone, hexanes and chloroform. The majority of the polymer was dissolved in the hexanes fraction. Therefore, the hexanes and chloroform fractions were combined and redissolved in chloroform. This solution was treated with diethylammonium dithiocarbamate to remove palladium salts after which the organic phase was extracted with water three times, dried over magnesium sulphate and concentrated to about 2 ml. This concentrated solution was precipitated into methanol and this precipitation was repeated twice.

(49) 67 mg (79%) of a deep blue metallic solid of formula P1 with purple reflection were obtained. GPC (chlorobenzene, 80 C.): Mn=15000, Mw=26000, PDI=1.7

(50) .sup.1H NMR (400 MHz, CDCl.sub.3, ): 8.2 (br s, 2H), 8.0 (br s, 1H), 7.9 (br s, 1 H), 7.8 (br s, 2H), 2.2 -2.0 (br m, 8H), 1.3-1.1 (br m, 112H). 0.89 (t, 12H)

(51) TABLE-US-00001 TABLE 1 Polymer Comonomer (Yield) .sub.max (film) Eg opt HOMO/LUMO I-NDT BT P1 639 1.81 5.4/ 3.6.sup.a)

Example 13

(52) ##STR00083##
The polymer P2 Has Been Synthesized in Analogy to Polymer P1
Preparation of Back-Contact, Top-Gate FETs

(53) Semiconducting compound or polymer is dissolved at a concentration of 0.75 wt % in orthodichlorobenzene and subsequently coated onto a PET-substrate with lithographically prepatterned gold contacts, serving as Source and Drain contact of the FET.

(54) The formulation is applied by spin coating (1200 rpm, 30 seconds). After the coating is completed, the substrate is immediately transferred onto a preheated hotplate and heated for 60 s at 90 C. Next the gate dielectric layer consisting of 4 wt % PS dissolved in propylene glycol monomethyl ether acetate (PGMEA) is spincoated on top of the organic semiconductor (2500 rpm, 30 seconds). 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 450 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.

(55) Electrical Characterization

(56) 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.

(57) The threshold voltage Um can be taken from the intersection of black dashed line in FIG. 1 with the X-axis portion (V.sub.GS).

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

(59) $\begin{array}{c}=\frac{m^2*2L}{C_G*W}\end{array}\begin{array}{c}{C}_G={\mathrm{.Math.}}_0*{\mathrm{.Math.}}_r\frac{1}{d}\end{array}\begin{array}{c}{U}_{\mathrm{th}}=-1*\frac{m}{b}\end{array}$$\begin{array}{c}\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=2,6 for Cytop and d=450 nm is the thickness of the dielectric. The W/L ratio is 25.

(60) TABLE-US-00002 TABLE 2 The following mobilities have been calculated for the respective compounds: Field-effect mobility Threshold voltage Compound [cm.sup.2/Vs] U.sub.TH [V] ON/OFF ratio P1 0.3 8 5E5 P2 0.006 4.5 2E4

(61) FIG. 1 shows a representative transfer characteristics of a FET fabricated from polymer P1 with VGS=10 V to 30 V at 0.5V step size with VDS=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).

(62) FIG. 2 shows a representative transfer characteristics of a FET fabricated from Polymer P2 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).