Thienothiophene-isoindigo

Abstract

Polymers containing at least one unit of formula ##STR00001##
wherein X.sup.1, X.sup.2 and X.sup.3 are independently from each other O, S or NR.sup.1, a process for their preparation, intermediates and electronic devices containing these polymers as semiconducting material.

Claims

1. A polymer, comprising: at least one unit of formula (1) ##STR00095## wherein X.sup.1, X.sup.2 and X.sup.3 are independently from each other S or NR.sup.1, A is ##STR00096## wherein X.sup.4 is S or NR.sup.1, and A1 can be substituted with one substituent R.sup.2, B is selected from the group consisting of ##STR00097## wherein X.sup.5 and X.sup.6 are independently from each other S or NR.sup.1, and B1, B2 and B3 can be substituted with one to three substituents R.sup.2, R.sup.1 is at each occurrence selected from the group consisting of C.sub.1-50-alkyl, C.sub.2-50-alkenyl and C.sub.2-50-alkynyl, wherein C.sub.1-50-alkyl, C.sub.2-50-alkenyl and C.sub.2-50-alkynyl can be 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.1-50-alkyl, C.sub.2-50-alkenyl and C.sub.2-50-alkynyl can be replaced by O or S, wherein R.sup.a is 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.5-6-cycloalkyl and C.sub.6-10-aryl, R.sup.Sia, R.sup.Sib and R.sup.Sic are 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.5-6-cycloalkyl, C.sub.6-10-aryl, [OSiR.sup.SidR.sup.Sie].sub.oR.sup.Sif, wherein o is an integer from 1 to 50, R.sup.Sid, R.sup.Sie, R.sup.Sif are independently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, [OSiR.sup.SigR.sup.Sih].sub.pR.sup.Sii, wherein p is an integer from 1 to 50, R.sup.Sig R.sup.Sih, R.sup.Sii are independently selected from the group consisting of H, C.sub.1-30-alkyl, C.sub.2-30-alkenyl, C.sub.2-30-alkynyl, C.sub.5-6-cycloalkyl, C.sub.6-10-aryl, OSi(CH.sub.3).sub.3, and R.sup.2 is at each occurrence selected from the group consisting of unsubstituted C.sub.1-30-alkyl and halogen, n is 0, 1, 2 or 3, m is 0, 1, 2 or 3, and L.sup.1 and are L.sup.2 are independently from each other and at each occurrence selected from the group consisting of C.sub.6-18-arylene, 5 to 20 membered heteroarylene, ##STR00098## wherein C.sub.6-18-arylene and 5 to 20 membered heteroarylene can be substituted with one to six substituents R.sup.3 at each occurrence 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, 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, and wherein ##STR00099## can be substituted with one or two substituents R.sup.4 at each occurrence 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 independently from each other and at each occurrence 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, and wherein C.sub.1-30-alkyl, C.sub.2-30-alkenyl and C.sub.2-30-alkynyl can be 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 can be replaced by O or S, C.sub.5-12-cycloalkyl can be 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 can be replaced by O, S, OC(O), CO, NR.sup.i or NR.sup.iCO, C.sub.6-18-aryl and 5 to 20 membered heteroaryl can be substituted with one to six substituents independently selected from the group consisting of C.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 independently from each other 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 OSi(CH.sub.3).sub.3, 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 C.sub.1-20-alkyl, C.sub.2-20-alkenyl and C.sub.2-20-alkynyl can be 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.l, NR.sup.k-C(O)R.sup.l, C(O)NR.sup.kR.sup.l, N[C(O)R.sup.k][C(O)R.sup.l], SR.sup.k, halogen, CN, and NO.sub.2; C.sub.5-8-cycloalkyl can be 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.l, N[C(O)R.sup.k][C(O)R.sup.l], SR.sup.k, halogen, CN, and NO.sub.2; C.sub.6-14-aryl and 5 to 14 membered heteroaryl can be substituted with one to five substituents independently selected from the group consisting of C.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.l, 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, wherein C.sub.1-10-alkyl, C.sub.2-10-alkenyl and C.sub.2-10-alkynyl can be 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 X.sup.1 is S, and X.sup.2 and X.sup.3 are NR.sup.1.

3. The polymer of claim 1, wherein A is ##STR00100## wherein X.sup.4 is S or NR.sup.1, and A1 can be substituted with one substituent R.sup.2, B is ##STR00101## wherein X.sup.5 and X.sup.6 are independently from each other S or NR.sup.1, and B2 can be substituted with one substituent R.sup.2, R.sup.1 is at each occurrence selected from the group consisting of C.sub.1-36-alkyl, C.sub.2-36-alkenyl and C.sub.2-36-alkynyl, wherein C.sub.1-36-alkyl, C.sub.2-36-alkenyl and C.sub.2-36-alkynyl can be 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 can be replaced by O or S, wherein R.sup.a is 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 and C.sub.6-10-aryl R.sup.Sia, 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, [OSiR.sup.SidR.sup.Sic].sub.oR.sup.Sif wherein o is an integer from 1 to 50, R.sup.Sid, R.sup.Sie, R.sup.Sif are independently selected from the group consisting of H, 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, [OSiR.sup.SigR.sup.Sih].sub.pR.sup.Sii, wherein p is an integer from 1 to 50, R.sup.Sig R.sup.Sih, R.sup.Siiare 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, OSi(CH.sub.3).sub.3, and R.sup.2 is at each occurrence selected from the group consisting of unsubstituted C.sub.1-30-alkyl and halogen.

4. The polymer of claim 1, wherein A is ##STR00102## wherein X.sup.4 is S and A1 is not substituted, B is ##STR00103## wherein X.sup.5 and X.sup.6 are S, and B2 is not substituted, and R.sup.1 is at each occurrence unsubstituted C.sub.1-36-alkyl.

5. The polymer of claim 1, wherein L.sup.1 and L.sup.2 are independently from each other and at each occurrence selected from the group consisting of 5 to 20 membered heteroarylene, and ##STR00104## wherein 5 to 20 membered heteroarylene can be substituted with one to six substituents R.sup.3 at each occurrence 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.Six and OH, and wherein ##STR00105## can be substituted with one or two substituents R.sup.4 at each occurrence 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 independently from each other and at each occurrence selected from the group consisting of H, 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, and wherein C.sub.1-30-alkyl, C.sub.2-30-alkenyl and C.sub.2-30-alkynyl can be 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 can be replaced by O or S, C.sub.5-12-cycloalkyl can be 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)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 can be replaced by O, S, OC(O), CO, NR.sup.i or NR.sup.iCO, C.sub.6-18-aryl and 5 to 20 membered heteroaryl can be substituted with one to six substituents independently selected from the group consisting of C.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 independently from each other 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 OSi(CH.sub.3).sub.3, 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 C.sub.1-20-alkyl, C.sub.2-20-alkenyl and C.sub.2-20-alkynyl can be 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.l, NR.sup.kC(O)R.sup.l, C(O)NR.sup.kR.sup.l, N[C(O)R.sup.k][C(O)R.sup.l], SR.sup.k, halogen, CN, and NO.sub.2; C.sub.5-8-cycloalkyl can be 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.l, N[C(O)R.sup.k][C(O)R.sup.l], SR.sup.k, halogen, CN, and NO.sub.2; C.sub.6-14-aryl and 5 to 14 membered heteroaryl can be substituted with one to five substituents independently selected from the group consisting of C.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.l, 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 C.sub.1-10-alkyl, C.sub.2-10-alkenyl and C.sub.2-10-alkynyl can be substituted with one to five substituents selected from the group consisting of halogen, CN and NO.sub.2.

6. The polymer of claim 1, wherein L.sup.1 and L.sup.2 are independently from each other and at each occurrence selected from the group consisting of 5 to 20 membered heteroarylene, and ##STR00106## wherein 5 to 20 membered heteroarylene is selected from the group consisting of ##STR00107## ##STR00108## 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 C.sub.1-20-alkyl, C.sub.2-20-alkenyl and C.sub.2-20-alkynyl can be 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.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; C.sub.5-8-cycloalkyl can be 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; C.sub.6-14-aryl and 5 to 14 membered heteroaryl can be substituted with one to five substituents independently selected from the group consisting of C.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; 5 to 12 membered ring system can be 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 C.sub.1-10-alkyl, C.sub.2-10-alkenyl and C.sub.2-10-alkynyl can be substituted with one to five substituents selected from the group consisting of halogen, CN and NO.sub.2, wherein 5 to 20 membered heteroarylene can be 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, and wherein ##STR00109## can be substituted with one or two substituents R.sup.4 at each occurrence 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.

7. The polymer of claim 1, wherein L.sup.1 and L.sup.2 are independently from each other and at each occurrence 5 to 20 membered heteroarylene, wherein 5 to 20 membered heteroarylene is selected from the group consisting of ##STR00110## wherein 5 to 20 membered heteroarylene is unsubstituted.

8. The polymer of claim 5, wherein n is 0, 1 or 2, and m is 0, 1 or 2.

9. A process for the preparation of the polymer of claim 1, wherein n is 0 and which are of formula (1-I) ##STR00111## which process comprises: treating a compound of formula (2) ##STR00112## wherein Y is at each occurrence I, Br, Cl or OS(O).sub.2CF.sub.3, and X.sup.1, X.sup.2, X.sup.3, A and B are as defined for the compound of formula (1) with m mol equivalents of a compound of formula (3)
Z.sup.a-L.sup.2-Z.sup.b(3) wherein L.sup.2 is as defined for the compound of formula (1), and Z.sup.a and Z.sup.b are independently selected from the group consisting of B(OZ.sup.1)(OZ.sup.2), SnZ.sup.1Z.sup.2Z.sup.3, ##STR00113## wherein Z.sup.1, Z.sup.2, Z.sup.3, Z.sup.4, Z.sup.5 and Z.sup.6 are independently from each other and at each occurrence H or C.sub.1-4-alkyl.

10. An electronic device, comprising: a polymer of claim 1.

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

12. A method of making a semiconductor, the method comprising: depositing a polymer according to claim 1 onto a substrate.

13. A method of transmitting electrons within a semiconductor material, the method comprising: passing electrons through a polymer according to claim 1, said polymer comprised within a semiconductor device.

Description

EXAMPLES

Example 1

(1) Preparation of Compound 3a

(2) ##STR00090##
Preparation of Compound 5a

(3) Compound 6a (5.00 g, 22.82 mmol, 1 equiv.), copper (0.07 g, 1.14 mmol, 5 mol %) copper(I)-iodide (0.22 g, 1.14 mmol, 5 mol %), potassium phosphate tribasic (9.69 g, 45.64 mmol, 2 equiv.) and 2-decyltetradecyl amine (12.11 g, 34.23 mmol, 1.5 equiv.) were heated with stirring in dimethyl aminoethanol (50 mL) at 80 C. for 48 hours. Upon cooling to room temperature, water and hexane were added. The aqueous layer was extracted several times with hexanes. The organic layers were combined, dried over MgSO.sub.4 and the solvent was removed by rotary evaporation. The crude product was passed through a small silica column using hexane as solvent to afford compound 5a as brown oil (1.74 g, 3.54 mmol, 15.5%). .sup.1H NMR (400 MHz, CDCl.sub.3); 7.36 (dd, J=5.3, 1.4 Hz, 1H), 6.05 (d, 1H, J=2.1 Hz), 3.56 (s, 1H), 3.13 (d, J=6.1 Hz, 2H), 1.29 (bm, 40H), 0.91 (m, 6H).

(4) Preparation of Compound 4a

(5) Dioxalyl chloride (0.50 g, 3.96 mmol, 1.3 equiv.) in DCM (10 mL) was added dropwise to a stirred solution of compound 5a (1.50 g, 3.05 mmol, 1 equiv.) in DCM (20 mL) at 10 C. After thirty minutes of stirring at 10 C., triethylamine (1.39 g, 13.72, 4.5 equiv.) was added and the solution was allowed to warm to room temperature overnight. Solvent and excess triethylamine were removed by rotary evaporation and the crude compound 4a was purified by column chromatography on silica with DCM as the eluent to afford the compound 4a as bright red solid (0.68 g, 1.24 mmol, 41%). .sup.1H NMR (400 MHz, CDCl.sub.3); 7.85 (d, J=5.3 Hz, 1H), 7.37 (d, J=5.1 Hz, 1H), 3.68 (d, J=7.7 Hz, 2H), 1.9 (m, 1H), 1.25 (bm, 40H), 0.88 (m, 6H).

(6) Preparation of Compound 3a

(7) A solution of compound 4a (0.60 g, 0.57 mmol, 1 equiv.) and Lawesson's reagent (0.11 g, 0.28 mmol, 0.5 equiv.) in o-xylene (20 mL) were heated at 60 C. for 2 hours. After cooling to room temperature the solvent was removed by rotary evaporation and the crude product purified by column chromatography on silica with hexane:DCM (3:1) as the eluent to afford compound 3a as a bright green solid (0.37 g, 0.35 mmol, 32%). .sup.1H NMR (400 MHz, CDCl.sub.3); 7.52 (d, J=5.2 Hz, 2H), 7.32 (d, J=5.2 Hz, 2H), 3.85 (d, J=7.7 Hz, 4H), 2.04 (m, 2H), 1.24 (bm, 80H), 0.90 (m, 12H).

Example 2

(8) Preparation of Compound 2a

(9) ##STR00091##

(10) N-bromosuccinimide (0.12 g, 0.69 mmol, 2.1 equiv.) in THF (1 mL) was added to a stirred solution of compound 3a (0.35 g, 0.33 mmol, 1 equiv.) in THF (20 mL) at 0 C. The reaction was monitored by TLC and quenched with water after half an hour, the product was extracted with ethyl acetate and the aqueous layer extracted several times with ethyl acetate. The organic layers were combined, dried over MgSO.sub.4 and the solvent removed by rotary evaporation to afford the crude compound 2a which was purified by column chromatography on silica using hexane: DCM (3:1) as the eluent to afford the compound 2a as dark green solid (0.31 g, 0.26 mmol, 77%). .sup.1H NMR (400 MHz, d.sub.2-TCE); 7.35 (s, 2H), 3.80 (d, J=7.7 Hz, 4H), 1.96 (m, 2H), 1.27 (bm 80H), 0.93 (m, 12H).

Example 3

(11) Preparation of Polymer Pa

(12) ##STR00092##

(13) Compound 2a (70 mg, 0.06 mmol, 1 equiv.) and 4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxabrolan-2-yl)benzothiadiazole (3a) (22 mg, 0.06 mmol, 1 equiv.) were added to a microwave vial. A thoroughly degassed solution of Aliquat 336 (1 drop) in toluene (1.5 mL) was subsequently added and the solution was further degassed with stirring for 30 minutes. Pd(P(Ph).sub.3).sub.4 (3 mg) was added and the solution was again degassed for 30 minutes. The microwave vial was sealed and heated to 80 C. with stirring and then 2M Na.sub.2CO.sub.3(aq) (0.3 mL) were added. The biphasic mixture was then heated with vigorous stirring at 120 C. for 3 days. After cooling to room temperature the contents of the microwave vial were poured into vigorously stirred methanol and the resulting polymeric precipitate was filtered. The filtrate was purified by Soxhlet extraction first with acetone (24 h), second with hexane (24 h), and third with chloroform (24 h). The chloroform fraction was stirred vigorously with aqueous sodium diethyldithiocarbamate at 60 C. for 2 hours to remove any residual catalytic metal impurities, after which the chloroform layer was separated and the solvent removed by rotary evaporation. The obtained polymeric material was purified further by recycling gel permeation chromatography (GPC) in chlorobenzene to afford the polymer Pa (45 mg, 57%) as dark purple/black solid. GPC (chlorobenzene, 80 C., polystyrene standard): M.sub.n=17 kDa, M.sub.w=27 kDa, PDI=1.6. UV-VIS-absorption spectrum: .sub.max: 926 nm (film) and 914 nm (solution). HOMO as determined by photoelectron spectroscopy in air (UV-PESA): 4.9 eV. HOMO as calculated by DFT/TD-DFT with a B3LYP/6-31 g*basis set: 4.7 eV. LUMO as determined from absorption onset in thin film UV-VIS spectra: 3.8 eV. LUMO as calculated by DFT/TD-DFT with a B3LYP/6-31 g*basis set: 3.5 eV. Eg as observed: 1.1 eV. Eg as calculated by DFT/TD-DFT with a B3LYP/6-31 g*basis set: 1.2 eV.

Example 4

(14) Preparation of Polymer Pb

(15) ##STR00093##

(16) Compound 2a (70 mg, 0.06 mmol, 1 equiv.) and 2,5-bis(trimethylstannyl)thiophene (24 mg, 0.06 mmol, 1 equiv) in chlorobenzene (1.0 mL) were added to a microwave vial. The solution was thoroughly degassed before the addition of Pd.sub.2(dba).sub.3 (2 mg) and P(o-Tol).sub.3 (2.5 mg). The solution was further degassed and the microwave vial sealed before heating in a microwave in successive intervals of 5 min at 100 C., 5 min at 140 C., 5 min at 160 C. and finally 20 min at 180 C. After cooling to room temperature the contents of the microwave vial were poured into vigorously stirred methanol, and the resulting polymeric precipitate was collected by filtration. The polymeric precipitate was purified by Soxhlet extraction first with acetone (24 h), second with hexane (24 h) and finally with chloroform (24 h). The chloroform fraction was stirred vigorously with aqueous sodium diethyldithiocarbamate at 60 C. for 2 hours to remove any residual catalytic metal impurities, after which the chloroform layer was separated and the solvent removed by rotary evaporation. The obtained polymeric material was further purified by recycling gel permeation chromatography (GPC) in chlorobenzene to afford the polymer Pb (31 mg, 47%) as deep purple/black solid. GPC (chlorobenzene, 80 C., polystyrene standard): M.sub.n=30 kDa, M.sub.w=67 kDa, PDI=2.3. UV-VIS-absorption spectrum: .sub.max: 909 nm (film) and 897 nm (solution). HOMO as determined by photoelectron spectroscopy in air (UV-PESA): 4.8 eV. HOMO as calculated by DFT/TD-DFT with a B3LYP/6-31 g*basis set: 4.6 eV. LUMO as determined from absorption onset in thin film UV-VIS spectra: 3.6 eV. LUMO as calculated by DFT/TD-DFT with a B3LYP/6-31 g*basis set: 3.3 eV. Eg as observed: 1.2 eV. Eg as calculated by DFT/TD-DFT with a B3LYP/6-31 g*basis set: 1.3 eV.

Example 5

(17) Preparation of Polymer Pc

(18) ##STR00094##

(19) Compound 2a (70 mg, 0.06 mmol, 1 equiv.) and 5,5-bis(trimethylstannyl)-2,2-bithiophene (28 mg, 0.06 mmol, 1 equiv) in chlorobenzene (1.0 mL) were added to a microwave vial. The solution was thoroughly degassed before the addition of Pd.sub.2(dba).sub.3 (2 mg) and P(o-Tol).sub.3 (2.5 mg). The solution was further degassed and the microwave vial sealed before heating in a microwave in successive intervals of 5 min at 100 C., 5 min at 140 C., 5 min at 160 C. and finally 20 min at 180 C. After cooling to room temperature the contents of the microwave vial were poured into vigorously stirred methanol, and the resulting polymeric precipitate was collected by filtration. The polymeric precipitate was purified by Soxhlet extraction first with acetone (24 h), second with hexane (24 h) and finally with chloroform (24 h). The chloroform fraction was stirred vigorously with aqueous sodium diethyldithiocarbamate at 60 C. for 2 hours to remove any residual catalytic metal impurities, after which the chloroform layer was separated and the solvent was removed by rotary evaporation. The obtained polymeric material was further purified by recycling gel permeation chromatography (GPC) in chlorobenzene to afford polymer Pc (42 mg, 60%) as deep purple/black solid. GPC (chlorobenzene, 80 C., polystyrene standard): M.sub.n=20 kDa, M.sub.w=41 kDa, PDI=2.1. UV-VIS-absorption spectrum: .sub.max: 875 nm (film) and 864 nm (solution). HOMO as determined by photoelectron spectroscopy in air (UV-PESA): 4.8 eV. HOMO as calculated by DFT/TD-DFT with a B3LYP/6-31 g*basis set: 4.6 eV. LUMO as determined from absorption onset in thin film UV-VIS spectra: 3.6 eV. LUMO as calculated by DFT/TD-DFT with a B3LYP/6-31 g*basis set: 3.2 eV. Eg as observed: 1.2 eV. Eg as calculated by DFT/TD-DFT with a B3LYP/6-31 g*basis set: 1.4 eV.

Example 6

(20) Preparation of Organic Field Effect Transistors Comprising the Polymer Pa, Pb, Respectively, Pc

(21) Organic field effect transistors (top-gate/bottom contact) were fabricated on glass substrates with Ti/Au (10 nm/30 nm) evaporated on photo-lithographically defined electrodes. The polymer Pa, Pb, respectively, Pc was deposited by spin coating from a 10 mg/mL dichlorobenzene solution and was annealed for 1 h at 100, 200 or 300 C., respectively. After annealing, the films were quenched on a cold metal surface and a 300 nm thick poly(methylmethacrylate) dielectric layer was spin-coated on top. A 20 nm thick gold layer was then evaporated through a shadow mask to define the transistor's top-gate. All fabrication steps were performed in an N.sub.2 glove box. The channel characteristics are: L=20 m, W=1 mm.

(22) Pa, Pb and Pc were stable up to annealing temperatures of 350 C. with no observable thermal transition.

(23) The saturation transfer curves of the organic field effect transistors comprising polymer Pa, Pb, respectively, Pc were measured at V.sub.d=60V using an Agilent 4155B Semiconductor Parameter Analyser (SPA) in a N.sub.2 glove box. The average values of the electron mobilities .sub.e, the hole mobilities .sub.h and the threshold voltages V.sub.th were determined from the square root of the saturation transfer curves and the results are summarized in table 1.

(24) TABLE-US-00001 TABLE 1 T.sub.anneal .sub.e .sub.h V.sub.th V.sub.th Polymer [ C.] [cm.sup.2/Vs] [cm.sup.2/Vs] (electrons) [V] (holes) [V] Pa 100 0.2 0.1 14 10 200 0.5 0.3 12 13 300 0.7 0.4 13 20 Pb 100 0.01 0.01 7 32 200 0.2 0.2 18 24 300 0.2 0.2 24 22 Pc 100 0.01 n/a.sup.a 3 200 0.1 0.4 18 25 300 0.1 0.4 11 21 .sup.anot-available.

(25) Pa, Pb, respectively, Pc exhibit good ambipolar properties, with improvements in hole and electron mobilities observed at high temperature annealing. The electron transport is favoured in Pa, whereas the hole transport is favoured Pc. Pb shows a very balanced hole and electron transport.