Thieno-indeno-monomers and polymers

Abstract

Polymers comprising at least one unit of formulae ##STR00001## and compounds of the formulae ##STR00002## wherein, in formulae 1, 1′, 2 and 2′ n is 0, 1, 2, 3 or 4 m is 0, 1, 2, 3 or 4 M1 and M2 are independently of each other an aromatic or heteroaromatic monocyclic or bicyclic ring system; 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.1-100-alkyl, C.sub.2-100-alkenyl, C.sub.2-100-alkynyl, C.sub.5-12-cycloalkyl, C.sub.6-18-aryl, a 5 to 20 membered heteroaryl, C(O)—C.sub.1-100-alkyl, C(O)—C.sub.5-12-cycloalkyl and C(O)—OC.sub.1-100-alkyl. R.sup.2, 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 heteroaryl, OR.sup.21, OC(O)—R.sup.21, C(O)—OR.sup.21, C(O)—R.sup.21, NR.sup.21R.sup.22, NR.sup.21—C(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, ##STR00003##

Claims

1. A polymer suitable as a semiconducting material, comprising a unit of formulae (1c): ##STR00100## wherein: X is S; Q is C; L.sup.2 is selected from the group consisting of C.sub.6-30-arylene, 5 to 30 membered heteroarylene, ##STR00101## C.sub.6-30-arylene and 5 to 30 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.31—C(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, ##STR00102## 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, 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, 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.i—C(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.i—C(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.i—CO, 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.i—C(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, R.sup.Siv, R.sup.Siw, 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 O—Si(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.6-10-aryl, and 5 to 14 membered heteroaryl, 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.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.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.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, 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, 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, R.sup.2, R.sup.2′ and R.sup.2″ are at each occurrence selected from the group consisting of hydrogen, unsubstituted C.sub.1-30-alkyl and halogen, R is at each occurrence unsubstituted C.sub.1-50-alkyl, C.sub.3-50-alkenyl, or C.sub.3-50-alkynyl, m is 0, 1, 2, 3 or 4, and p is 2 to 1000.

2. The polymer according to claim 1, wherein: R.sup.2, R.sup.2′ and R.sup.2″ are at each occurrence hydrogen, and R is at each occurrence C.sub.1-36-alkyl.

3. The polymer of claim 1, wherein: L.sup.2 is selected from the group from the group consisting of C.sub.6-30-arylene and 5 to 30 membered heteroarylene, and ##STR00103## C.sub.6-30-arylene and 5 to 30 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.31—C(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, ##STR00104## 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, 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, 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.i—C(O)R.sup.j, C(O)—NR.sup.iR.sup.j, N[C(O)R][C(O)R.sup.i], 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.1-30n-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.i—C(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.i—CO, 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.i—C(O)R.sup.j, C(O)—NR.sup.iR.sup.j, N[C(O)R][C(O)R.sup.j], SR.sup.i, halogen, CN, SiR.sup.SivR.sup.SiwR.sup.Six and NO.sub.2, R.sup.Siv, R.sup.Siw, 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.5-8-cycloalkyl, phenyl and O—Si(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, 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.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.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.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, 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 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.

4. The polymer of claim 3, wherein: L.sup.2 is selected from the group from the group consisting of C.sub.6-30-arylene and 5 to 30 membered heteroarylene, and ##STR00105## C.sub.6-30-arylene and 5 to 30 membered heteroarylene is selected from the group consisting of ##STR00106## ##STR00107## ##STR00108## 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, 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.s—C(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.s—C(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.s—C(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.s—C(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, 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, 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, C.sub.6-30-arylene and 5 to 30 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, ##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, R.sup.41 is at each occurrence C.sub.1-30-alkyl, and X′ is S.

5. The polymer of claim 4, wherein: L.sup.2 is selected from the group consisting of ##STR00110## ##STR00111## and X′ is S.

6. The polymer of claim 5, wherein: L.sup.2 is selected from the group consisting of ##STR00112##

7. The polymer of claim 1, wherein m is 0, 1 or 2.

8. An electronic device, comprising a semiconducting layer that comprises the polymer of claim 1.

Description

EXAMPLES

(1) General Experimental Details for Synthetic Part

(2) Methods and materials: All reagents from commercial sources were used without further purification. Solvents were dried and purified using standard techniques. Most of the compounds were characterized by NMR, usually at room temperature. High-resolution mass spectrometry (HRMS) data was recorded using a Thermo Scientific-LTQ Velos Orbitrap MS in positive atmospheric pressure photoionization (+APPI) mode. UV-Vis spectra were recorded in a Varian Cary 100 spectrophotometer. Thermogravimetric analysis (TGA) was performed under N.sub.2 using Bruker TGA-IR TG209F1 with a ramp of 10° C./min. Differential Scanning Calorimetry (DSC) was run on DSC-204F1-phoenix. Number average (Mn) and weight-average (Mw) molecular weight were determined by Agilent Technologies 1200 series GPC running in chlorobenzene at 80° C., using two PL mixed B columns in series and/or in trichlorobenzene at 150° C. and calibrated against narrow polydispersity polystyrene standards. Flash chromatography (FC) was performed on silica gel. Microwave experiments were performed in a Biotage initiator V 2.3.

(3) Synthetic Details and Characterization

(4) ##STR00087## ##STR00088##

Example 1

Synthesis of 1-bromo-2-chloro-4-(dibromomethyl)-5-fluorobenzene (J-2)

(5) 1-bromo-2-chloro-5-fluoro-4-methylbenzene (20.0 g, 90 mmol), NBS (48.06 g, 270 mmol) and BPO

(6) (2.18 g, 9 mmol) dissolved in 1,2-dichloroethane (250 ml). Stirred at reflux until the starting material was consumed monitored by GC-MS and quenched with water and extracted with ethyl acetate. Organic phases collected and dried over magnesium sulfate, filtered and concentrated under vacuum. Purified via column chromatography on silica gel with 1:1 ethyl acetate:hexane

(7) as eluent to afford a brown oil. Yield: 32.50 g (95%)

(8) .sup.1H NMR (700 MHz, CDCl.sub.3) δ 7.91 (d, J=7.1 Hz, 1H), 7.36 (d, J=9.1 Hz, 1H), 6.80 (s, 1H).

Example 2

Synthesis of 4-bromo-5-chloro-2-fluorobenzaldehyde (J-3)

(9) 1-bromo-2-chloro-4-(dibromomethyl)-5-fluorobenzene (34.0 g, 89.2 mmol), dissolved in formic acid (500 ml) and stirred at reflux overnight. Allowed to cool to room temperature and poured into water. The resulting solid was collected, washed with water until the washings were no longer acidic and dried to afford a white solid. Yield: 15.32 g (72%)

(10) .sup.1H NMR (700 MHz, CDCl.sub.3) δ 10.25 (s, 1H), 7.92 (d, J=6.5 Hz, 1H), 7.53 (d, J=9.2 Hz, 1H).

Example 3

Synthesis of Ethyl 6-bromo-5-chlorobenzo[b]thiophene-2-carboxylate (J-4)

(11) 4-bromo-5-chloro-2-fluorobenzaldehyde (22.40 g, 94.4 mmol) was dissolved in DMSO (200 ml). Triethylamine (39.5 ml, 283.2 mmol) and ethyl thioglycolate (12.4 ml, 113.2 mmol) were added and the mixture stirred at 80° C. The reaction was quenched with water when the starting material was totally disappeared monitored by GC-MS and extracted with ethyl acetate. The organic phases were collected, dried over magnesium sulfate, filtered and concentrated under vacuum. The product was purified by column chromatography on silica gel with 5:1 hexane:dichloromethane as eluent. Resulting in a yellowish solid. Yield: 24.74 g (82%)

(12) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.14 (s, 1H), 7.96 (s, 1H), 7.94 (s, 1H), 4.43 (q, 2H), 1.44 (t, 3H).

Example 4

Synthesis of Diethyl 6,6′-(2,5-dimethyl-1,4-phenylene)bis(5-chlorobenzo[b]thiophene-2-carboxylate) (J-5)

(13) Ethyl 6-bromo-5-chlorobenzo[b]thiophene-2-carboxylate (2 g, 6.29 mmol), 2,2′-(2,5-dimethyl-1,4-phenylene)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (0.90 g, 2.52 mmol) was dissolved in toluene/H.sub.2O (15 mL/3 mL) in a 50 mL flask and digassed with argon, then Pd.sub.2(dba).sub.3 (0.09 g, 0.25 mmol), (o-tol).sub.3P (0.09 g, 0.76 mmol), K.sub.3PO.sub.4 (8.01 g, 37.74 mmol) and 2 drops of aliquat were added into the mixture and digassed with argon again. The mixture was subjected to reflux for 24 h. After cooling to room temperature, the reaction mixture was extracted with chloroform, and the organic phase was collected and then passed through a short silicon gel column quickly and then recrystalized from chloroform/methanol, resulting in a white solid. Yield: 1.06 g (72%)

(14) .sup.1H NMR (500 MHz, CDCl.sub.3) δ 8.05 (s, 2H), 8.01 (d, J=1.9 Hz, 2H), 7.86 and 7.77 (2 s (rotamers), 2H), 7.12 (s, 2H), 4.45 (q, 4H), 2.15 (s, 6H), 1.45 (t, J=7.2 Hz, 6H).

Example 5

Synthesis of 6,6′-(2,5-dimethyl-1,4-phenylene)bis(5-chlorobenzo[b]thiophene-2-carboxylic acid) (3-6)

(15) Diethyl 6,6′-(2,5-dimethyl-1,4-phenylene)bis(5-chlorobenzo[b]thiophene-2-carboxylate) (10 g, 17.14 mmol) was dissolved in hot ethanol (300 mL) and potassium hydroxide (9.62 g, 171.4 mmol) in water (80 mL) added. The suspension was heated at reflux overnight. After cooling slightly, 6 N HCl (60 mL) was added portionwise. The residual solid was filtered, washed with water and dried to give an off-white solid. Yield: 9.04 g (98%)

(16) .sup.1H NMR (700 MHz, DMSO) δ 13.68 (s, 2H), 8.25 (d, J=1.9 Hz, 2H), 8.13 (d, J=2.1 Hz, 2H), 8.11 and 8.07 (2 s (rotamers), 2H), 2.06 (s, 6H).

Example 6

Synthesis of 6,6′-(2,5-dimethyl-1,4-phenylene)bis(5-chlorobenzo[b]thiophene) (3-7)

(17) 6,6′-(2,5-dimethyl-1,4-phenylene)bis(5-chlorobenzo[b]thiophene-2-carboxylic acid) (8 g, 15.21 mmol) and copper powder (2.24 g, 35 mmol) were suspended in quinoline (120 mL) and heated at 185° C. overnight. After cooling down to rt, the mixture was filtered and the solid was washed with chloroform and the combined organic solutions was washed with 2 N HCl twice. The residue was purified by chromatography on silica with chloroform/hexane to afford a white solid. Yield: 5.53 g (83%)

(18) .sup.1H NMR (700 MHz, DMSO, 80° C.) δ 8.10 (s, 2H), 8.02 and 7.98 (2 s (rotamers), 2H), 7.85 (d, J=5.3 Hz, 2H), 7.48 (d, J=5.3 Hz, 2H), 7.13 (s, 2H), 2.07 (s, 6H).

Example 7

Synthesis of (J-8)

(19) A mixture of 6,6′-(2,5-dimethyl-1,4-phenylene)bis(5-chlorobenzo[b]thiophene) (1 g, 2.28 mmol), Pd(OAc).sub.2 (0.15 g, 0.228 mmol), IPr.HCl (0.19 g, 0.456 mmol), K.sub.2CO.sub.3 (1.26 g, 9.12 mmol) and NMP (25 mL) in a 50 mL flask was purged with nitrogen for 5 min. The mixture was then kept in an oil bath at 170° C. overnight. After cooling to room temperature, the solution was extracted with chloroform and washed with water. The solvents of the organic phase were removed under reduced pressure. The residue was subjected to chromatography on silica gel, eluting with hexane/chloroform to afford a white solid. Yield: 0.69 g (83%)

(20) .sup.1H NMR (700 MHz, DMSO) δ 8.51 (s, 2H), 8.15 (s, 2H), 8.05 (s, 2H), 7.70 (d, J=5.3 Hz, 2H), 7.46 (d, J=5.3 Hz, 2H), 4.10 (s, 4H).

Example 8

Synthesis of Compound (J-9)

(21) To a suspension of compound 8 (1 g, 2.73 mmol) in anhydrous DMSO (50 ml) was added sodium tert-butoxide (2.63 g, 27.3 mmol) in parts. The reaction mixture was heated at 80° C. for 1 h, followed by the addition of 1-bromohexadecane (5 g, 16.38 mmol) dropwise. After complete addition, the resultant mixture was heated at 85° C. for 12 h. After cooling to room temperature, water was added to quench the reaction, then the solution was extracted with dichloromethane and washed with water. The solvents of the organic phase were removed under reduced pressure. The residue was subjected to chromatography on silica gel, eluting with hexane to afford a light-yellow solid. Yield: 3.45 g (81%)

(22) .sup.1H NMR (700 MHz, CD.sub.2Cl.sub.2) δ 8.24 (s, 2H), 7.79 (s, 2H), 7.75 (s, 2H), 7.46 (d, J=5.3 Hz, 2H), 7.39 (d, J=5.3 Hz, 2H), 2.13-2.11 (m, 8H), 0.96-1.36 (m, 104H), 0.90-0.86 (m, 12H), 0.83-0.69 (m, 8H).

Example 9

Synthesis of Compound (J-10)

(23) To a suspension of compound 8 (1 g, 2.73 mmol) in anhydrous DMSO (50 ml) was added sodium tert-butoxide (2.63 g, 27.3 mmol) in parts. The reaction mixture was heated at 80° C. for 1 h, followed by the addition of 2-Ethylhexyl bromide (3.16 g, 16.38 mmol) dropwise. After complete addition, the resultant mixture was heated at 85° C. for 12 h. After cooling to room temperature, water was added to quench the reaction, then the solution was extracted with dichloromethane and washed with water. The solvents of the organic phase were removed under reduced pressure. The residue was subjected to chromatography on silica gel, eluting with hexane to afford a light-yellow solid. Yield: 2.23 g (71%)

(24) .sup.1H NMR (700 MHz, CD.sub.2Cl.sub.2) δ 8.20 (s, 2H), 7.78-7.75 (m, 2H), 7.74 (d, J=3.1 Hz, 2H), 7.41 (d, J=5.3 Hz, 2H), 7.36-7.33 (d, 2H), 2.18-1.95 (m, 8H), 1.02-0.41 (m, 60H).

(25) ##STR00089## ##STR00090##

(26) ##STR00091## ##STR00092## ##STR00093##

(27) The used di-bromo-co-monomers are commercially available:

(28) ##STR00094##

Example 10

Synthesis of Intermediate (J-11)

(29) To a suspension of compound J-9 (1 g, 0.79 mmol) in anhydrous THF (30 ml) and cooled to −78° C., then nBuLi (2.73 mmol) was added dropwisely. The reaction mixture was stirred at −78° C. for 1 h, then the temperature was rised to room temperature and cooled again to −10° C. followed by the addition of Me.sub.3SnCl (2.73 mmol) dropwise. After complete addition, the resultant mixture was slowly warmed up to rt and stirred overnight. Water was added to quench the reaction, then the solution was extracted with ethyl acetate and concentrated. The mixture was subjected to chromatography on Al.sub.2O.sub.3, eluting with hexane to afford J-11 as a light-yellow oil. Yield: 1.09 g (87%) .sup.1H NMR (500 MHz, CD.sub.2Cl.sub.2) δ 8.23 (s, 2H), 7.76 (s, 2H), 7.73 (s, 2H), 7.45 (s, 2H), 2.13-2.11 (m, 8H), 0.96-1.36 (m, 104H), 0.90-0.86 (m, 12H), 0.83-0.69 (m, 8H), 0.44 (t, 18H).

Example 11

Synthesis of Intermediate (J-12)

(30) To a suspension of compound J-10 (0.64 g, 0.79 mmol) in anhydrous THF (30 ml) and cooled to −78° C., then nBuLi (2.73 mmol) was added dropwisely. The reaction mixture was stirred at −78° C. for 1 h, then the temperature was rised to room temperature and cooled again to −10° C. followed by the addition of Me.sub.3SnCl (2.73 mmol) dropwise. After complete addition, the resultant mixture was slowly warmed up to rt and stirred overnight. Water was added to quench the reaction, then the solution was extracted with ethyl acetate and concentrated. The mixture was subjected to chromatography on Al.sub.2O.sub.3, eluting with hexane to afford a light-yellow solid. Yield: 0.77 g (85%)

(31) .sup.1H NMR (500 MHz, CD.sub.2Cl.sub.2) δ 8.24 (s, 2H), 7.77 (s, 2H), 7.75 (s, 2H), 7.48 (s, 2H), 2.13-1.36 (m, 8H), 0.90-0.69 (m, 60H), 0.44 (t, 18H).

Examples 12-19

Synthesis of Polymers P-1 to P-8

(32) A 2.5 mL microwave vial was charged with bis(trimethylstannyl) monomer J-10 or J-12 (0.233 mmol), 1 eq. of dibrominated monomer (corresponding (fluorinated)benzothiadiazole or thienothiophene), 2 mol % of tris(dibenzylideneacetone)dipalladium(0) and 8 mol % of tri(o-tolyl) phosphine. The vial was sealed and chlorobenzene (1 mL) was added. The obtained solution was degassed with argon during 30 minutes. The vial was subjected to the following reaction conditions in the microwave reactor: 2 minutes at 100° C., 2 minutes at 120° C., 5 minutes at 140° C., 5 minutes at 160° C. and 40 minutes at 180° C. The polymer was end-capped by addition of 0.1 eq. of 2-bromothiophene before the reaction mixture was resubmitted to the microwave reactor, 1 minute at 100° C., 1 minute at 120° C., 2 minutes at 140° C. and 5 minutes at 160° C. The polymeric solution was cooled down and 0.1 eq. of 2-(trimethylstannyl)thiophene was added by syringe. The reaction vial was subjected to the previously mentioned temperature scheme to finalize the end-capping reaction. After reaction, the crude polymer was precipitated in methanol and then further purified by Soxhlet extractions with acetone, hexane and chloroform during 24 hours each. Remaining palladium residues were removed by treating a polymeric chloroform solution with an aqueous sodium diethyldithiocarbamate solution for 2 hours at 50° C. under vigorous stirring. Afterwards the organic phase was separated from the aqueous phase and washed several times with water. The polymeric solution was concentrated under reduced pressure and precipitated into cold methanol. The polymer was filtered off and dried under high vacuum for at least 24 hours.

(33) Polymer P-1: .sup.1H NMR (500 MHz, CDCl.sub.3) δ 8.73 (br, 2H), 8.27 (br, 2H), 8.03 (br, 2H), 7.88 (br, 2H), 7.76 (br, 2H), 2.13-2.11 (br, 8H), 0.96-1.36 (br, 104H), 0.90-0.86 (br, 12H), 0.83-0.69 (br, 8H);

(34) Polymer P-2: .sup.1H NMR (500 MHz, CDCl.sub.3) δ 8.77 (br, 2H), 8.71 (br, 2H), 8.28 (br, 3H), 7.90 (br, 2H), 7.77 (br, 2H), 2.13-2.11 (br, 8H), 0.96-1.36 (br, 104H), 0.90-0.86 (br, 12H), 0.83-0.69 (br, 8H);

(35) Polymer P-3: .sup.1H NMR (500 MHz, CDCl.sub.3) δ 8.75 (br, 2H), 8.32 (br, 2H), 7.93 (br, 2H), 7.79 (br, 2H), 2.13-2.11 (br, 8H), 0.96-1.36 (br, 104H), 0.90-0.86 (br, 12H), 0.83-0.69 (br, 8H);

(36) Polymer P-4: .sup.1H NMR (500 MHz, CDCl.sub.3) δ 8.14 (br, 2H), 7.69 (br, 4H), 7.49 (br, 2H), 7.46 (br, 2H), 2.13-2.11 (br, 8H), 0.96-1.36 (br, 104H), 0.90-0.86 (br, 12H), 0.83-0.69 (br, 8H);

(37) Polymer P-5: .sup.1H NMR (500 MHz, CDCl.sub.3) δ 8.74 (br, 2H), 8.27 (br, 2H), 8.02 (br, 2H), 7.86 (br, 2H), 7.74 (br, 2H), 2.13-2.11 (br, 8H), 0.96-1.36 (br, 104H), 0.90-0.86 (br, 12H), 0.83-0.69 (br, 8H), 0.44-0.48 (br, 18H);

(38) Polymer P-6: .sup.1H NMR (500 MHz, CDCl.sub.3) δ 8.76 (br, 2H), 8.73 (br, 2H), 8.25 (br, 3H), 7.93 (br, 2H), 7.77 (br, 2H), 2.13-2.11 (br, 8H), 0.96-1.36 (br, 104H), 0.90-0.86 (br, 12H), 0.83-0.69 (br, 8H), 0.44-0.48 (br, 18H);

(39) Polymer P-7: .sup.1H NMR (500 MHz, CDCl.sub.3) δ 8.75 (br, 2H), 8.34 (br, 2H), 7.92 (br, 2H), 7.79 (br, 2H), 2.13-2.11 (br, 8H), 0.96-1.36 (br, 104H), 0.90-0.86 (br, 12H), 0.83-0.69 (br, 8H), 0.44-0.48 (br, 18H);

(40) Polymer P-8: .sup.1H NMR (500 MHz, CDCl.sub.3) δ 7.95 (br, 2H), 7.83 (br, 2H), 7.71 (br, 2H), 7.40 (br, 2H), 7.23 (br, 2H), 2.13-2.11 (br, 8H), 0.96-1.36 (br, 104H), 0.90-0.86 (br, 12H), 0.83-0.69 (br, 8H), 0.44-0.48 (br, 18H).

(41) GPC Data:

(42) TABLE-US-00001 Mn Mw Polymer KDa KDa PDI P-1 41.6 56.6 1.36 P-2 55.2 82.7 1.50 P-3 49.0 74.2 1.51 P-4 29.8 60.9 2.04 P-5 169.5 327.0 1.93 P-6 60.0 129.1 2.15 P-7 59.3 140.9 2.37 P-8 69.5 181.6 2.61

(43) ##STR00095##

Example 20

Synthesis of Intermediate (J-13)

(44) Intermediate J-13 can be obtained commercially [1197732-41-4] or by literature described methods from 1,4-dibromo-2,3-dimethyl-benzene [75024-22-5].

Example 21

Synthesis of Intermediate (J-14)

(45) 56.3 mmol (18.0 g) of compound J-4, 28.15 mmol (9.604 g) of compound J-13, 0.67 mmol (0.633 g) tris-(dibenzylideneacetone)-dipalladium(0) [51364-51-3] and 1.61 mmol (0.481 g) tri-tertbutyl-phosphonium-tetrafluoroborate [131274-22-1] were added to a 250 ml 3-necked-flask equipped with a thermometer, reflux condenser with argon inlet and a septum. The system was evacuated and refilled with argon two times. Then 150 ml of dry and degassed tetrahydrofuran was added to the reaction flask. After dissolution of the starting material at 50° C., a degassed solution of 83 mmol (18 g) potassium phosphate in 3.8 ml of water was added and the reaction mixture was heated to reflux and stirred for 4 hours. The reaction mixture was allowed to cool to rt over night, where the product precipitated. The reaction mixture was filtered, washed with THF and then with water and then dried to give the crude J-14 which was used directly in the next step.

(46) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.06 (s, 2H), 8.02 (s, 2H), 7.86 and 7.79 (2 s (rotamers), 2H), 7.13 (s, 2H), 4.45 (q, 4H), 2.13 (s, 6H), 1.46 (t, 6H).

Example 22

Synthesis of Intermediate (J-15)

(47) 20 mmol (11.5 g) of compound J-14 was suspended in 300 ml of ethanol, and then a solution of 5.5 g of KOH in 20 ml of water was added to the suspension. The suspension was then refluxed over night. The suspension was cooled to rt and then poured into 4 M HCl. The precipitate was filtered and washed well with water and then dried to give crude J-15 which was used directly in the next step.

(48) .sup.1H NMR (400 MHz, DMSO-D.sub.6) δ 8.28 (s, 2H), 8.15 (s, 2H), 8.10 and 8.06 (2 s (rotamers), 2H), 7.13 (s, 2H), 2.06 (s, 6H).

Example 23

Synthesis of Intermediate (J-16)

(49) 11.82 mmol (6.400 g) of compound J-15 was suspended in 25 ml of quinoline. Then 1.728 g of copper powder was added and the reaction mixture was heated for 8 hours at 185° C. The copper was allowed to settle to the bottom of the flask, and the solution was decanted and the product precipitated with ethanol to give crude J-16 which was used directly in the next step.

(50) .sup.1H NMR (400 MHz, DMSO-D.sub.6) δ 8.14 (s, 2H), 8.05 and 8.01 (2 s (rotamers), 2H), 7.90 (d, 2H), 7.51 (d, 2H), 7.11 (s, 2H), 2.06 (s, 6H).

Example 24

Synthesis of Intermediate (J-17)

(51) 7.282 mmol (3.20 g) of compound J-16, 29.129 mmol (4.066 g) potassium carbonate, 0.728 mmol (0.163 g) palladium(II)acetate and 1.456 mmol (0.619 g) 1,3-Bis(2,6-diisopropylphenyl)imidazoliumchloride [250285-32-6] have been loaded to a 50 ml 3-necked-flask equipped with a thermometer, reflux condenser with argon inlet and a septum. Then 20 ml of anhydrous N-methylpyrrolidone were added under nitrogen and the reaction mixture was stirred for 7 hours at 170° C. Then the mixture was cooled to rt and water was added. The precipitate was filtered and washed with water and then dried to give crude J-17, which was used directly in the next step. The product was too insoluble to measure an NMR.

Example 25

Synthesis of Intermediate (J-18)

(52) 3.82 mmol (1.46 g) of compound J-17 were suspended in 20 ml of dry dimethylsulfoxide. Then 38 mmol (3.67 g) of sodium tert-butoxide were added under nitrogen. The reaction mixture was heated to 85° C. for 1 hour. Then a solution of 23 mmol (8.075 g) 1-iodohexadecane in 5 ml of dimethylsulfoxide was added over a period of 2 hours. The reaction mixture was stirred over night at 85° C. The mixture was cooled to rt and water was added. The mixture was then extracted with heptane. The heptane solution was washed with water and dried over MgSO.sub.4 and then the solvent was evaporated. The product was purified by column chromatography on silica gel. Then the product was recrystallized from ethyl acetate to get compound J-18. .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.18 (s, 2H), 7.85 (s, 2H), 7.69 (s, 2H), 7.44 (d, 2H), 7.39 (d, 2H), 2.46 (br t, 4H), 2.10 (br t, 4H), 1.35-1.02 (m, 104H), 0.90 (t, 12H), 0.62-0.58 (br, 8H).

(53) ##STR00096##

Example 26

Synthesis of Intermediate (J-19)

(54) 0.791 mmol (1.0 g) of compound J-18 were added to a 100 ml 3-necked-flask equipped with a thermometer, reflux condenser with argon inlet and a septum. The system was evacuated and refilled with argon two times. Then 50 ml of dry and degassed tetrahydrofuran was added to the reaction flask. After dissolution of the starting material, the temperature was lowered to −78° C. Then 2.689 mmol (0.996 ml) of 2.7M n-butyllithium solution in heptane were added slowly via a syringe. After stirring for 15 minutes, the reaction mixture was allowed to come to room temperature for 1 hour. Then the temperature was reduced to −20° C. and 2.689 mmol (2.689 ml) of 1M trimethyltinchloride solution in (in hexanes) were added via a syringe. The reaction mixture was stirred then overnight at room temperature. The reaction was quenched by the addition of water and the product was extracted with ethylacetate. The organic phase was dried over MgSO.sub.4 and evaporated. The residue was recrystallized from ethyl acetate and then from heptane to yield 400 mg of compound J-19.

(55) .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) δ 8.21 (s, 2H), 7.88 (s, 2H), 7.73 (s, 2H), 7.50 (s, 2H), 2.50 (br t, 4H), 2.13 (br t, 4H), 1.35-1.04 (m, 104H), 0.90 (t, 12H), 0.64-0.55 (br, 8H), 0.49 (t, 18H).

Example 27

Synthesis of Polymer (P-9)

(56) 0.019 mmol (30.2 mg) of compound J-19 and 0.019 mmol (5.6 mg) of 4,7-dibromo-benzo[c]-1,2,5-thiadiazole [15155-41-6], 0.001 mmol (0.9 mg) of tris-(dibenzylideneacetone)-dipalladium(0) [51364-51-3] and 0.004 mmol (1.2 mg) of tri-(o-tolyl)-phosphine [6163-58-2] were charged to a 10 ml 3-necked-flask equipped with a thermometer, reflux condenser with argon inlet and a septum. The system was evacuated and refilled with argon for five times. Via a syringe 2 ml of degassed chlorobenzene was added. The reaction mixture was then brought to reflux for 22 hours. The reaction mixture turned to intense red color. The reaction mixture was added to 20 ml of acetone, where the polymer precipitated. The polymer was filtered and the residue washed with acetone. The polymer was taken up into toluene and refluxed for 3 hours with an aqeuous solution of sodium-diethyl-dithiocarbamate to remove Pd residues. The solution was cooled to rt, separated the phases and the organic phase was washed twice with deionized water. The toluene phase was added to aceton to precipitate the polymer once again. After filtration, the polymer was added to a soxhlet thimble and extracted first with acetone, then hexanes, and finally with toluene. The aceton fraction contained no polymer. The hexanes and toluene fractions were added to aceton, where the polymer precipitated. The hexane fraction yielded 22 mg of the polymer P-9 (GPC data (trichlorobenzene, 150° C.): Mw 32′665 PDI 2.21), and the toluene fraction yielded 7 mg of the polymer P-9.

(57) ##STR00097##

Example 28

Synthesis of Intermediate (3-20)

(58) 64 mmol (10.0 g) of 2,6-dimethylnaphthalene were dissolved in 100 ml dichloromethane and 20 mg of iodine were added. 139 mmol (22.21 g) bromine were added dropwise over 7 hours at 21° C. The mixture was then stirred over night at rt. The organic phase was washed with aqeuous sodiumthiosulphate and water, dried and evaporated. The crude product was recrystallized from ethanol to give compound J-20.

(59) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.22 (d, 2H), 7.44 (d, 2H), 2.65 (s, 6H).

Example 29

Synthesis of Intermediate (J-21)

(60) 33.4 mmol (10.50 g) of compound J-20, 94.5 mmol (24.00 g) bis(pinacolato)diborone [73183-34-3], 268 mmol (26.52 g) potassium acetate and 2.006 mmol (1.47 g) Pd(dppf)Cl.sub.2 [72287-26-4] were placed in a 250 ml 3-necked-flask equipped with a thermometer, reflux condenser with argon inlet and a septum. The system was evacuated and refilled with argon for five times. Via a syringe 80 ml of degassed dimethylformamide was added. The reaction mixture was then heated and stirred at 110° C. for 48 hours. The mixture was cooled to rt, and water was added and the product was extracted with heptane. The organic phase was dried and evaporated. The product was recrystallized from isopropanol to get compound J-21.

(61) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 8.03 (d, 2H), 7.27 (d, 2H), 2.60 (s, 6H), 1.49 (s, 24H).

Example 30

Synthesis of Intermediate (J-22)

(62) Intermediate J-22 was synthesized from compound J-4 and J-21 according to compound J-14 described in example 21.

(63) .sup.1H NMR (300 MHz, DMSO-D.sub.6) δ 8.41 (s, 2H), 8.29 (s, 2H), 8.18 and 8.09 (2 s (rotamers), 2H), 7.40 (d, 2H), 7.12 (d, 2H), 4.40 (q, 4H), 2.10 (s, 6H), 1.37 (t, 6H).

Example 31

Synthesis of Intermediate (J-23)

(64) Intermediate J-23 was synthesized from compound J-22 according to compound J-15 described in example 22.

(65) .sup.1H NMR (300 MHz, DMSO-D.sub.6) δ 8.40 (s, 2H), 8.21 (s, 2H), 8.08 (s, 2H), 7.39 (d, 2H), 7.13 (d, 2H), 2.12 (s, 6H).

Example 32

Synthesis of Intermediate (J-24)

(66) Intermediate J-24 was synthesized from compound J-23 according to compound J-16 described in example 23.

(67) .sup.1H NMR (300 MHz, DMSO-D.sub.6) δ 8.25 (s, 2H), 8.09 and 8.00 (2 s (rotamers), 2H), 7.94 (d, 2H), 7.57 (d, 2H), 7.37 (d, 2H), 7.13 (d, 2H), 2.12 (s, 6H).

Example 33

Synthesis of Intermediate (J-25)

(68) Intermediate J-25 was synthesized from compound J-24 according to compound J-17 described in example 24.

(69) .sup.1H NMR (400 MHz, DMSO-D.sub.6) δ 9.23 (s, 2H), 9.02 (d, 2H), 8.16 (s, 2H), 7.99 (d, 2H), 7.81 (d, 2H), 7.52 (d, 2H), 4.24 (s, 4H).

Example 34

Synthesis of Intermediate (J-26)

(70) Intermediate J-26 was synthesized from compound J-25 according to compound J-18 described in example 25.

(71) .sup.1H NMR (300 MHz, CDCl.sub.3) δ 8.89 (d, 2H), 8.87 (s, 2H), 7.86 (s, 2H), 7.73 (d, 2H), 7.50 (d, 2H), 7.42 (d, 2H), 2.19-2.11 (br, 8H), 1.35-0.95 (m, 104H), 0.89 (t, 12H), 0.75-0.60 (br, 8H).

(72) ##STR00098##

Example 35

Synthesis of Intermediate (J-27)

(73) Intermediate 3-27 was synthesized from compound J-26 according to compound J-19 described in example 26.

(74) .sup.1H NMR (300 MHz, CDCl.sub.3) δ 8.89 (d, 2H), 8.87 (s, 2H), 7.85 (s, 2H), 7.73 (d, 2H), 7.51 (s, 2H), 2.19-2.11 (br, 8H), 1.50-1.00 (m, 104H), 0.90 (t, 12H), 0.73-0.62 (br, 8H), 0.49 (t, 18H).

Example 36

Synthesis of Polymer (P-10)

(75) Polymer P-10 was synthesized from 0.274 mmol (449 mg) of compound J-27 and 0.274 mmol (80.5 mg) of 4,7-dibromo-benzo[c]-1,2,5-thiadiazole [15155-41-6], according to polymer P-9 described in example 27. Soxhlet extraction gave 79 mg polymer P-10 from hexane fraction (GPC data (trichlorobenzene, 150° C.): Mw 27′139, PDI 2.23) and 257 mg polymer P-10 from toluene fraction (GPC data (trichlorobenzene, 150° C.): Mw 78′162, PDI 2.28).

Example 37

Synthesis of Polymer P-11 (Same Structure as Polymer P-1 Above) Via Direct Heteroarylation Polymerization

(76) ##STR00099##

(77) 0.032 mmol (40 mg) of compound J-9 and 0.032 mmol (12 mg) of 4,7-dibromo-benzo[c]-1,2,5-thiadiazole [15155-41-6] were placed together with 10% Pd(Herrmann) catalyst and 15% tri(ortho-methoxy-phenyl)phosphine, 2 equivalents of pivalic acid, 3 equivalents of potassiumcarbonate and 2 ml dimethylacetamide in a vial and degassed with argon. Then the reaction mixture was heated and stirred vigorously for 48 hours at 140° C. The polymer P-11 was precipitated with water, filtered and washed with water. Then the polymer was purified and fractionated in analogy to experiments 12-19 described above. The chloroform fraction gave a polymer P-11 with the following GPC data (chlorobenzene at 80° C.): Mw 52′300, PDI 1.41.

Application Examples A-1 to A-4

(78) Fabrication and electrical characterization of organic field-effect transistors (OFET) based on the polymers P-1, P-2, P-3, and P-4

(79) The polymers are dissolved at a concentration of 0.75 wt % in dichlorobenzene. Back-contact, Top-gate FETs are fabricated from each formulation according to the following procedure:

(80) A PEN-substrate with lithographically pre-patterned gold contacts, serving as source and drain contact of the FET are used as substrates. 100 μl of the formulation is coated by a standard blade coater yielding a homogenous layer of the semiconductor over the entire substrate. After the coating is completed, the substrate is immediately transferred onto a preheated hotplate and heated for 30 s at 90° C. Next the gate dielectric layer consisting of Polystyrene 4 wt % dissolved in PGMEA is spin-coated on top of the organic semiconductor (2500 rpm, 30 s). After spin-coating of the dielectric, the substrate is again transferred to the hotplate and annealed for another 5 Min at 90° C. The thickness of the dielectric layer is 420 nm measured by profilometer. Finally 50 nm thick, shadow-mask patterned gold gate electrodes are deposited by vacuum evaporation to complete FETs in the BCTG-configuration.

(81) The mobility μ is calculated from the root representation of the transfer characteristic curve (solid grey curve) in the saturation region. The slope m is determined from the dashed black line in the respective transfer characteristics. The dashed black line is fitted to a region of the square root representation of the drain current ID such that a good correlation to the linear slope of the root representation is obtained.

(82) The threshold voltage U.sub.Th can be taken from the intersection of black dashed line with the X-axis portion (V.sub.GS).

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

(84) $\mu =\frac{m^2*2L}{C_G*W}{C}_G={\mathrm{.Math.}}_0*{\mathrm{.Math.}}_r\frac{1}{d}{U}_{\mathrm{Th}}=-1*\frac{m}{b}\mathrm{ON}/\mathrm{OFF}=\frac{I_D\max }{I_D\min }$

(85) where ε.sub.0 is the vacuum permittivity of 8.85×10.sup.−12 As/Vm. ε.sub.r=2,6 for Polystyrene and d is the thickness of the dielectric. The width over length ratio W/L is 10.

(86) FIG. 1 show representative transfer characteristics of an FET fabricated from polymer P-1 with V.sub.GS=30 V to −30 V at 0.5 V step size with V.sub.DS=−30 V. 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).

(87) FIG. 2 show representative transfer characteristics of an FET fabricated from polymer P-2 with V.sub.GS=30 V to −30 V at 0.5 V step size with V.sub.DS=−30 V. 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).

(88) FIG. 3 show representative transfer characteristics of an FET fabricated from polymer P-3 with V.sub.GS=30 V to −30 V at 0.5 V step size with V.sub.DS=−30 V. 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).

(89) FIG. 4 show representative transfer characteristics of an FET fabricated from polymer P-4 with V.sub.GS=30 V to −30 V at 0.5 V step size with V.sub.DS=−30 V. 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).

(90) The following mobilities, threshold voltages and ON/OFF ratios are the average values obtained for the respective compound. The number of TFTs entering the calculation of the average is given in the table:

(91) TABLE-US-00002 Field-effect Threshold Number mobility μ voltage U.sub.TH ON/OFF Compound of TFTs [cm.sup.2/Vs] [V] ratio P-1 20 2.0 −11 4E6 P-2 19 1.4 −8.5 4E6 P-3 18 1.4 −10.7 2E6 P-4 13 7E−4 −8.9 8E2