Thieno-indeno-monomers and polymers

18:

• A polymer, comprising at least one unit of formulae:
• wherein:
• X, Y are S;
• Q is C;
• L1 and L2 are independently from each other and at each occurrence selected from the group consisting of C6-30-arylene, 5 to 30 membered heteroarylene,
• C6-30-arylene and 5 to 30 membered heteroarylene can be substituted with one to six substituents R3 at each occurrence selected from the group consisting of C1-30-alkyl, C2-30-alkenyl, C2-30-alkynyl, C5-12-cycloalkyl, C6-18-aryl and 5 to 20 membered heteroaryl, OR31, OC(O)—R31, C(O)—OR31, C(O)—R31, NR31R32, NR31—C(O)R32, C(O)—NR31R32, N[C(O)R31][C(O)R32], SR31, halogen, CN, SiRSivRSiwRSix and OH,
• can be substituted with one or two substituents R4 at each occurrence selected from the group consisting of C1-30-alkyl, C2-30-alkenyl, C2-30-alkynyl, C5-12-cycloalkyl, C6-18-aryl and 5 to 20 membered heteroaryl, C(O)—R41, C(O)—NR41R42, C(O)—OR41 and CN,
• R31, R32, R41 and R42 are independently from each other and at each occurrence selected from the group consisting of H, C1-30-alkyl, C2-30-alkenyl, C2-30-alkynyl, C5-12-cycloalkyl, C6-18-aryl and 5 to 20 membered heteroaryl,
• C1-30-alkyl, C2-30-alkenyl and C2-30-alkynyl can be substituted with one to ten substituents independently selected from the group consisting of C5-8-cycloalkyl, C6-14-aryl, 5 to 14 membered heteroaryl, ORi, OC(O)—Rj, C(O)—ORi, C(O)—Ri, NRiRj, NRi—C(O)Rj, C(O)—NRiRj, N[C(O)Ri][C(O)Rj], SRi, halogen, CN, SiRSivRSiwRSix and NO2;
• and at least two CH2-groups, but not adjacent CH2-groups of C1-30-alkyl, C2-30-alkenyl and C2-30-alkynyl can be replaced by O or S,
• C5-12-cycloalkyl can be substituted with one to six substituents independently selected from the group consisting of C1-20-alkyl, C2-20-alkenyl and C2-20-alkynyl, C5-8-cycloalkyl, C6-14-aryl, 5 to 14 membered heteroaryl, ORi, OC(O)—Rj, C(O)—ORi, C(O)—Ri, NRiRj, NRi—C(O)Rj, C(O)—NRiRj, N[C(O)Ri][C(O)Rj], SRi, halogen, CN, SiRSivRSiwRSix and NO2;
• and one or two CH2-groups, but not adjacent CH2-groups, of C5-12-cycloalkyl can be replaced by O, S, OC(O), CO, NRi or NRi—CO,
• C6-18-aryl and 5 to 20 membered heteroaryl can be substituted with one to six substituents independently selected from the group consisting of C1-20-alkyl, C2-20-alkenyl, C2-20-alkynyl, C5-8-cycloalkyl, C6-14-aryl, 5 to 14 membered heteroaryl, ORi, OC(O)—Rj, C(O)—ORi, C(O)—Ri, NRiRj, NRi—C(O)Rj, C(O)—NRiRj, N[C(O)Ri][C(O)Rj], SRi, halogen, CN, SiRSivRSiwRSix and NO2,
• RSiv, RSiw, RSix are independently from each other selected from the group consisting of H, C1-20-alkyl, C2-20-alkenyl, C2-20-alkynyl, C5-6-cycloalkyl, phenyl and O—Si(CH3)3,
• Ri and Rj are independently selected from the group consisting of H, C1-20-alkyl, C2-20-alkenyl, C2-20-alkynyl, C5-8-cycloalkyl, C6-10-aryl, and 5 to 14 membered heteroaryl,
• C1-20-alkyl, C2-20-alkenyl and C2-20-alkynyl can be substituted with one to five substituents selected from the group consisting of C5-6-cycloalkyl, C6-10-aryl, 5 to 10 membered heteroaryl, ORk, OC(O)—Rl, C(O)—ORk, C(O)—Rk, NRkRl, NRk—C(O)Rl, C(O)—NRkRl, N[C(O)Rk][C(O)Rl], SRk, halogen, CN, and NO2,
• C5-8-cycloalkyl can be substituted with one to five substituents selected from the group consisting of C1-10-alkyl, C2-10-alkenyl, C2-10-alkynyl, C5-6-cycloalkyl, C6-10-aryl, 5 to 10 membered heteroaryl, ORk, OC(O)—Rl, C(O)—ORk, C(O)—Rk, NRkRl, NRk—C(O)Rl, C(O)—NRkRl, N[C(O)Rk][C(O)Rl], SRk, halogen, CN, and NO2,
• C6-14-aryl and 5 to 14 membered heteroaryl can be substituted with one to five substituents independently selected from the group consisting of C1-10-alkyl, C2-10-alkenyl, C2-10-alkynyl, C5-6-cycloalkyl, C6-10-aryl, 5 to 10 membered heteroaryl, ORk, OC(O)—Rl, C(O)—ORk, C(O)—Rk, NRkRl, NRk-C(O)Rl,
• C(O)—NRkRl, N[C(O)Rk][C(O)Rl], SRk, halogen, CN, and NO2,
• Rk and Rl are independently selected from the group consisting of H, C1-10-alkyl,
• C2-10-alkenyl and C2-10-alkynyl, C1-10-alkyl, C2-10-alkenyl and C2-10-alkynyl can be substituted with one to five substituents selected from the group consisting of halogen, CN and NO2,
• R2, R2′ and R2″ are at each occurrence selected from the group consisting of hydrogen, unsubstituted C1-30-alkyl and halogen,
• R is at each occurrence unsubstituted C1-50-alkyl, C3-50-alkenyl, or C3-50-alkynyl,
• m is 0, 1, 2, 3 or 4, and
• p is 2 to 1000.

20:

• The polymers of claim 18, wherein:
• L1and L2 are independently from each other and at each occurrence selected from the
• group consisting of C6-30-arylene and 5 to 30 membered heteroarylene,
• and
• C6-30-arylene and 5 to 30 membered heteroarylene can be substituted with one to six substituents R3 at each occurrence selected from the group consisting of C1-30-alkyl, C2-30-alkenyl, C2-30-alkynyl, C5-12-cycloalkyl, C6-18-aryl and 5 to 20 membered heteroaryl, OR31, OC(O)—R31, C(O)—OR31, C(O)—R31, NR31R32, NR31—C(O)R32, C(O)—NR31R32, SR31, halogen, CN, SiRSivRSiwRSix and OH,
• can be substituted with one or two substituents R4 at each occurrence selected from the group consisting of C1-30-alkyl, C2-30-alkenyl, C2-30-alkynyl, C5-12-cycloalkyl, C6-18-aryl and 5 to 20 membered heteroaryl, C(O)—R41, C(O)—NR4lR42, C(O)—OR41 and CN,
• R31, R32, R41 and R42 are independently from each other and at each occurrence selected from the group consisting of H, C1-30-alkyl, C2-30-alkenyl, C2-30-alkynyl, C5-12-cycloalkyl, C6-18-aryl and 5 to 20 membered heteroaryl,
• C1-30-alkyl, C2-30-alkenyl and C2-30-alkynyl can be substituted with one to ten substituents independently selected from the group consisting of C5-8-cycloalkyl, C6-14-aryl, 5 to 14 membered heteroaryl, ORi, OC(O)—Rj, C(O)—ORi, C(O)—Ri, NRiRj, NRi—C(O)Rj, C(O)—NRiRj, N[C(O)Ri][C(O)Rj], SRi, halogen, CN, SiRSivRSiwRSix and NO2;
• and at least two CH2-groups, but not adjacent CH2-groups of C1-30-alkyl, C2-30-alkenyl and C2-30-alkynyl can be replaced by O or S,
• C5-12-cycloalkyl can be substituted with one to six substituents independently selected from the group consisting of C1-20-alkyl, C2-20-alkenyl and C2-20-alkynyl, C5-8-cycloalkyl, C6-14-aryl, 5 to 14 membered heteroaryl, ORi, OC(O)—Rj, C(O)—ORi, C(O)—Ri, NRiRj, NRi—C(O)Rj, C(O)—NRiRj, N[C(O)Ri][C(O)Rj], SRi, halogen, CN, SiRSivRSiwRSix and NO2;
• and one or two CH2-groups, but not adjacent CH2-groups, of C5-12-cycloalkyl can be replaced by O, S, OC(O), CO, NRi or NRi—CO,
• C6-18-aryl and 5 to 20 membered heteroaryl can be substituted with one to six substituents independently selected from the group consisting of C1-20-alkyl, C2-20-alkenyl, C2-20-alkynyl, C5-8-cycloalkyl, C6-14-aryl, 5 to 14 membered heteroaryl, ORi, OC(O)—Rj, C(O)—ORi, C(O)—Ri, NRiRj, NRi—C(O)Rj, C(O)—NRiRj, N[C(O)R][C(O)Rj], SRi, halogen, CN, SiRSivRSiwRSix and NO2,
• RSiv, RSiw, RSix are independently from each other selected from the group consisting of H, C1-20-alkyl, C2-20-alkenyl, C2-20-alkynyl, C5-8-cycloalkyl, phenyl and O—Si(CH3)3,
• Ri and Rj are independently selected from the group consisting of H, C1-20-alkyl, C2-20-alkenyl, C2-20-alkynyl, C5-8-cycloalkyl, C6-14-aryl, and 5 to 14 membered heteroaryl,
• C1-20-alkyl, C2-20-alkenyl and C2-20-alkynyl can be substituted with one to five substituents selected from the group consisting of C5-6-cycloalkyl, C6-10-aryl, 5 to 10 membered heteroaryl, ORk, OC(O)—Rl, C(O)—ORk, C(O)—Rk, NRkRl, NRk—C(O)Rl, C(O)—NRkRl, N[C(O)Rk][C(O)Rl], SRk, halogen, CN, and NO2,
• C5-8-cycloalkyl can be substituted with one to five substituents selected from the group consisting of C1-10-alkyl, C2-10-alkenyl, C2-10-alkynyl, C5-6-cycloalkyl, C6-10-aryl, 5 to 10 membered heteroaryl, ORk, OC(O)—Rl, C(O)—ORk, C(O)—Rk, NRkRl, NRk—C(O)Rl, C(O)—NRkRl, N[C(O)Rk][C(O)Rl], SRk, halogen, CN, and NO2,
• C6-14-aryl and 5 to 14 membered heteroaryl can be substituted with one to five substituents independently selected from the group consisting of C1-10-alkyl, C2-10-alkenyl, C2-10-alkynyl, C5-6-cycloalkyl, C6-10-aryl, 5 to 10 membered heteroaryl, ORk, OC(O)—Rl, C(O)—ORk, C(O)—Rk, NRkRl, NRk—C(O)Rl, C(O)—NRkRl, N[C(O)Rk][C(O)Rl], SRk, halogen, CN, and NO2,
• Rk and Rl are independently selected from the group consisting of H, C1-10-alkyl, C2-10-alkenyl and C2-10-alkynyl, and
• C1-10-alkyl, C2-10-alkenyl and C2-10-alkynyl can be substituted with one to five substituents selected from the group consisting of halogen, CN and NO2.

21:

• The polymer of claim 20, wherein:
• L1 and L2 are independently from each other and at each occurrence selected from the group consisting of C6-30-arylene and 5 to 30 membered heteroarylene
• and
• C6-30-arylene and 5 to 30 membered heteroarylene is selected from the group consisting of
• R104 and R105 are independently and at each occurrence selected from the group consisting of H, C1-20-alkyl, C2-20-alkenyl, C2-20-alkynyl, C5-8-cycloalkyl, C6-14-aryl, and 5 to 14 membered heteroaryl, or R104 and R105, if attached to the same atom, together with the atom, to which they are attached, form a 5 to 12 membered ring system,
• C1-20-alkyl, C2-20-alkenyl and C2-20-alkynyl can be substituted with one to five substituents selected from the group consisting of C5-6-cycloalkyl, C6-10-aryl, 5 to 10 membered heteroaryl, ORs, OC(O)—Rt, C(O)—ORs, C(O)—Rs, NRsRt, NRs—C(O)Rt,
• C(O)—NRsRt, N[C(O)Rs][C(O)Rt], SRs, halogen, CN, and NO2,
• C5-8-cycloalkyl can be substituted with one to five substituents selected from the group consisting of C1-10-alkyl, C2-10-alkenyl, C2-10-alkynyl, C5-6-cycloalkyl, C6-10-aryl, 5 to 10 membered heteroaryl, ORs, OC(O)—Rt, C(O)—ORs, C(O)—Rs, NRsRt, NRs—C(O)Rt, C(O)—NRsRt, N[C(O)Rs][C(O)Rt], SRs, halogen, CN, and NO2,
• C6-14-aryl and 5 to 14 membered heteroaryl can be substituted with one to five substituents independently selected from the group consisting of C1-10-alkyl, C2-10-alkenyl,
• C2-10-alkynyl, C5-6-cycloalkyl, C6-10-aryl, 5 to 10 membered heteroaryl, ORs, OC(O)—Rt, C(O)—ORs, C(O)—Rs, NRsRt, NRs—C(O)Rt, C(O)—NRsRt, N[C(O)Rs][C(O)Rt], SRs, halogen, CN, and NO2,
• 5 to 12 membered ring system can be substituted with one to five substituents selected from the group consisting of C1-10-alkyl, C2-10-alkenyl, C2-10-alkynyl, C5-6-cycloalkyl, C6-10-aryl, 5 to 10 membered heteroaryl, ORs, OC(O)—Rt, C(O)—ORs, C(O)—Rs, NRsRt, NRs—C(O)Rt, C(O)—NRsRt, N[C(O)Rs][C(O)Rt], SRs, halogen, CN, and NO2,
• Rs and Rt are independently selected from the group consisting of H, C1-10-alkyl, C2-10-alkenyl and C2-10-alkynyl,
• C1-10-alkyl, C2-10-alkenyl and C2-10-alkynyl can be substituted with one to five substituents selected from the group consisting of halogen, CN and NO2,
• C6-30-arylene and 5 to 30 membered heteroarylene can be substituted with one to six substituents R3 at each occurrence selected from the group consisting of C1-30-alkyl and halogen,
• can be substituted with one or two substituents R4 at each occurrence
• selected from the group consisting of C1-30-alkyl, C(O)—R41, C(O)—OR41 and CN,
• R41 is at each occurrence C1-30-alkyl, and
• X′ is S.

22:

• The polymer of claim 21, wherein:
• L1 and L2 are independently from each other selected from a group consisting of
• and
• X′ is S.

25:

• A process for preparing the polymer of claim 18, the process comprising reacting a compound of one of formulae (3a)-(3g):
• with a compound of formula (10):
• wherein
• Z* is at each occurrence I, Br, Cl, O—S(O)2CF3 or H,
• Za and Zb are independently selected from the group consisting of B(OZ1)(OZ2), SnZ1Z2Z3,
• Z1, Z2, Z3, Z4, Z5 and Z6 are independently from each other and at each occurrence H or C1-4-alkyl, and
• Za and Zb are Br if Z* is H.

26:

• A compound of one of formulae (3a)-(3g):
• wherein:
• X, Y are S;
• Q is C;
• R2, R2′ and R2″ are at each occurrence selected from the group consisting of hydrogen, unsubstituted C1-30-alkyl and halogen, and
• R is at each occurrence unsubstituted C1-50-alkyl, C3-50-alkenyl, or C3-50-alkynyl.