Phenanthro[9,10-B]furan polymers and small molecules for electronic applications

A polymer comprising a repeating unit of formula

• wherein
• A1′ and A2′ are each independently of formula
• wherein a, b, and c are each independently 0, 1, 2, or 3,
• Y, Y15, Y16 and Y17 are each independently
• R1 and R2 are each independently H, F, C1-C18 alkyl, C1-C18 alkyl which is substituted by E′ and/or interrupted by D′, C6-C24 aryl, C6-C24 aryl which is substituted by G′, C2-C20 heteroaryl, C2-C20 heteroaryl which is substituted by G′, or
• R1 and R2 form together a group
• where
• R205, R206, R206′, R207, R208, R208′, R209 and R210 are each independently H, C1-C18 alkyl, C1-C18 alkyl which is substituted by E′ and/or interrupted by D′, C1-C18 alkoxy, or C1-C18 alkoxy which is substituted by E′ and/or interrupted by D′, C1-C18 fluoroalkyl, C6-C24 aryl, C6-C24 aryl which is substituted by G′, C2-C20 heteroaryl, C2-C20 heteroaryl which is substituted by G′, C2-C18 alkenyl, C2-C18 alkynyl, C7-C25 aralkyl, C7-C25 aralkyl which is substituted by G′;
• CN, or —CO—R28,
• D′ is —CO—, —COO—, —S—, —SO—, —SO2—, —O—, —NR65—, —SiR70R71—, —POR72—, —CR63═CR64—, or —C≡C—,
• E′ is —OR69, —SR69, —NR65R66, —COR68, —COOR67, —CONR65R66, —CN, CF3, or halogen,
• G′ is E′, C1-C18 alkyl, or C1-C18 alkyl which is interrupted by —O—,
• R28 is H;
• C6-C18 aryl;
• C6-C18 aryl which is substituted by C1-C18 alkyl, or C1-C18 alkoxy;
• C1-C18 alkyl;
• or C1-C18 alkyl which is interrupted by —O—,
• R63 and R64 are each independently C6-C18 aryl;
• C6-C18 aryl which is substituted by C1-C18 alkyl, or C1-C18 alkoxy;
• C1-C18 alkyl;
• or C1-C18 alkyl which is interrupted by —O—;
• R65 and R66 are each independently C6-C18aryl;
• C6-C18 aryl which is substituted by C1-C18 alkyl, or C1-C18 alkoxy;
• C1-C18 alkyl;
• or C1-C18 alkyl which is interrupted by —O—;
• or
• R65 and R66 together form a five or six membered ring,
• R67 is C6-C18 aryl;
• C6-C18 aryl which is substituted by C1-C18 alkyl, or C1-C18 alkoxy;
• C1-C18 alkyl;
• or C1-C18 alkyl which is interrupted by —O—,
• R68 is H;
• C6-C18 aryl;
• C6-C18aryl which is substituted by C1-C18 alkyl, or C1-C18 alkoxy;
• C1-C18 alkyl;
• or C1-C18 alkyl which is interrupted by —O—,
• R69 is C6-C18 aryl;
• C6-C18 aryl, which is substituted by C1-C18 alkyl, or C1-C18 alkoxy;
• C1-C18 alkyl;
• or C1-C18 alkyl which is interrupted by —O—,
• R70 and R71 are each independently C1-C18 alkyl, C6-C18 aryl, or C6-C18 aryl, which is substituted by C1-C18 alkyl, and
• R72 is C1-C18 alkyl, C6-C18 aryl, or C6-C18 aryl, which is substituted by C1-C18 alkyl;
• p is 0 or 1;
• q is 0 or 1;
• A1 and A2 are each independently a group of formula
• where a is 0, 1, 2, or 3;
• b is 0, 1, 2, or 3;
• c is 0, 1, 2, or 3;
• and R10 is hydrogen, halogen, cyano, C1-C25 alkyl, C1-C25 alkyl which is substituted one or more times by E″ and/or interrupted one or more times by D″,
• COO—C1-C18 alkyl, C4-C18 cycloalkyl group, C4-C18 cycloalkyl group, which is substituted by G″, C2-C18 alkenyl, C2-C18 alkynyl, C1-C18 thioalkoxy, C1-C18 alkoxy, C1-C18 alkoxy which is substituted by E″ and/or interrupted by D″, C7-C25 aralkyl, C7-C25 aralkyl, which is substituted by G″, or a group of formulae IVa to IVm,
• where
• R22 to R26 and R29 to R58 each independently represent H, halogen, cyano, C1-C25 alkyl, C1-C25 alkyl which is substituted by E″ and/or interrupted by D″, C6-C24 aryl, C6-C24 aryl which is substituted by G″, C2-C20 heteroaryl, C2-C20 heteroaryl which is substituted by G″, a C4-C18 cycloalkyl group, a C4-C18 cycloalkyl group, which is substituted by G″, C2-C18 alkenyl, C2-C18 alkynyl, C1-C18 alkoxy, C1-C18 alkoxy which is substituted by E″ and/or interrupted by D″, C7-C25 aralkyl, or C7-C25 aralkyl, which is substituted by G″,
• R27 and R28 are each independently hydrogen, C1-C25 alkyl, halogen, cyano or C7-C25 aralkyl, or R27 and R28 together represent alkylene or alkenylene which are optionally both bonded via oxygen and/or sulfur to the thienyl residue and which optionally both have up to 25 carbon atoms,
• R59 is hydrogen, C6-C18 aryl;
• C6-C18 aryl which is substituted by C1-C18 alkyl, or C1-C18 alkoxy;
• or C1-C25 alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms;
• or C7-C25 arylalkyl,
• D″ is —CO—, —COO—, —S—, —O—, or —NR112″—,
• E″ is C1-C8 thioalkoxy, C1-C8 alkoxy, CN, —NR112″R113″, —CONR112″R113″, or halogen,
• G″ is E″, or C1-C18 alkyl, and
• R112″ and R113″ are each independently H;
• C6-C18 aryl;
• C6-C18 aryl which is substituted by C1-C18 alkyl, or C1-C18 alkoxy;
• C1-C18 alkyl;
• or C1-C18 alkyl which is interrupted by —O—;
• R214 and R215 are each independently hydrogen, C1-C18 alkyl, C6-C24 aryl, C2-C20 heteroaryl, —CN or COOR216;
• R216 is C1-C25 alkyl, C1-C25 haloalkyl, C7-C25 arylalkyl, C6-C24 aryl or C2-C20 heteroaryl;
• A3, A4, A5 and A5′ are each independently a group of formula -[Ar4]k′-[Ar5]l-[Ar6]r-[Ar7]z-, where k′ is 0, 1, 2, or 3;
• 1 is 0, 1, 2, or 3;
• r is 0, 1, 2, or 3;
• and z is 0, 1, 2, or 3;
• and
• Ar1, Ar2, Ar3, Ar4, Ar5, Ar6 and Ar7 are each independently selected from the group consisting of the following formulae:
• where X1 is —O—, —S—, —NR8—, —Si(R11)(R11′)—, —Ge(R11)(R11′)—, —C(R7)(R7′)—, —C(═O)—, —C(═CR104R104′)—,
• where X1′ is S, O, NR107—, —Si(R117)(R117′)—, —Ge(R117)(R117′)—, —C(R108)(R109)—, —C(═O)—, —C(═CR104R104′)—,
• where
• R3 and R3′ are each independently hydrogen, halogen, halogenated C1-C25 alkyl, cyano, C1-C25 alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms;
• C7-C25 arylalkyl, or C1-C25 alkoxy;
• R104 and R104′ are each independently hydrogen, cyano, COOR103, C1-C25 alkyl, or C6-C24 aryl or C2-C20 heteroaryl,
• R4, R4′, R5, R5′, R6 and R6′ are each independently hydrogen, halogen, halogenated C1-C25 alkyl, cyano, C1-C25 alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms;
• C7-C25 arylalkyl, or C1-C25 alkoxy;
• R7, R7′, R9 and R9′ are each independently hydrogen, C1-C25 alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms;
• or C1-C25 arylalkyl,
• R8 and R8′ are each independently hydrogen, C6-C18 aryl;
• C6-C18 aryl which is substituted by C1-C18 alkyl, or C1-C18 alkoxy;
• or C1-C25 alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms;
• or C7-C25 arylalkyl,
• R11 and R11″ are each independently C1-C25 alkyl, C7-C25 arylalkyl, or a phenyl group, which is optionally substituted one to three times with C1-C8 alkyl and/or C1-C8 alkoxy;
• R12 and R12′ are each independently hydrogen, halogen, cyano, C1-C25 alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms, C1-C25 alkoxy, C7-C25 aryalkyl, or
• wherein R13 is a C1-C10 alkyl group, or a tri(C1-C8 alkyl)silyl group;
• or
• R104 and R104′ are each independently hydrogen, C1-C18 alkyl, C6-C10 aryl, which is optionally substituted by G, or C2-C8 heteroaryl, which is optionally substituted by G,
• R105, R105′, R106 and R106′ are each independently hydrogen, halogen, cyano, C1-C25 alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms;
• C7-C25 arylalkyl, or C1-C18 alkoxy,
• R107 is hydrogen, C7-C25 arylalkyl, C6-C18 aryl;
• C6-C18 aryl which is substituted by C1-C18 alkyl, or C1-C18 alkoxy;
• C1-C18perfluoroalkyl;
• C1-C25 alkyl;
• which is optionally interrupted by —O—, or —S—;
• or —COOR103;
• R108 and R109 are each independently H, C1-C25 alkyl, C1-C25 alkyl which is substituted by E and/or interrupted by D, C7-C25 arylalkyl, C6-C24 aryl, C6-C24 aryl which is substituted by G, C2-C20 heteroaryl, C2-C20 heteroaryl which is substituted by G, C2-C18 alkenyl, C2-C18 alkynyl, C1-C18 alkoxy, C1-C18 alkoxy which is substituted by E and/or interrupted by D, or C7-C25 aralkyl, or
• R108 and R109 together form a group of formula ═CR110R111, wherein
• R110 and R111 are each independently H, C1-C18 alkyl, C1-C18 alkyl which is substituted by E and/or interrupted by D, C6-C24 aryl, C6-C24 aryl which is substituted by G, or C2-C20 heteroaryl, or C2-C20 heteroaryl which is substituted by G, or
• R108 and R109 together form a five or six membered ring, which is optionally substituted by C1-C18 alkyl, C1-C18 alkyl which is substituted by E and/or interrupted by D, C6-C24 aryl, C6-C24 aryl which is substituted by G, C2-C20 heteroaryl, C2-C20 heteroaryl which is substituted by G, C2-C18 alkenyl, C2-C18 alkynyl, C1-C18 alkoxy, C1-C18 alkoxy which is substituted by E and/or interrupted by D, or C7-C25 aralkyl,
• D is —CO—, —COO—, —S—, —O—, or —NR112′—,
• E is C1-C8 thioalkoxy, C1-C8 alkoxy, CN, —NR112′R113′, —CONR112′R113′, or halogen,
• G is E, or C1-C18 alkyl, and
• R112′ and R113′ are each independently H;
• C6-C18 aryl;
• C6-C18 aryl which is substituted by C1-C18 alkyl, or C1-C18 alkoxy;
• C1-C18 alkyl;
• or C1-C18 alkyl which is interrupted by —O—,
• R115 and R115′ are each independently hydrogen, halogen, cyano, C1-C25 alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms, C1-C25 alkoxy, C7-C25 arylalkyl, or
• wherein R116 is a C1-C10 alkyl group, or a tri(C1-C8alkyl)silyl group;
• R117 and R117′ are each independently C1-C25 alkyl group, C7-C25 arylalkyl, or a phenyl group, which is optionally substituted one to three times with C1-C8 alkyl and/or C1-C8 alkoxy;
• R118, R119, R120 and R121 each independently hydrogen, halogen, halogenated C1-C25 alkyl, cyano, C1-C25 alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms;
• C7-C25 arylalkyl, or C1-C25 alkoxy;
• R122 and R122′ are each independently hydrogen, C6-C18 aryl;
• C6-C18 aryl which is substituted by C1-C18 alkyl, or C1-C18 alkoxy;
• or C1-C25 alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms;
• or C7-C25 arylalkyl,
• R201 is selected from the group consisting of hydrogen, a C1-C100 alkyl group, —COOR103, a C1-C100 alkyl group substituted by one or more halogen atoms, hydroxyl groups, nitro groups, —CN, or C6-C18 aryl groups and/or interrupted by —O—, —COO—, —OCO— or —S—;
• a C7-C25 arylalkyl group, a carbamoyl group, a C5-C12 cycloalkyl group, which is optionally substituted one to three times with C1-C100 alkyl and/or C1-C100 alkoxy, a C6-C24 aryl group, which is optionally substituted one to three times with C1-C100 alkyl, C1-C100 thioalkoxy, and/or C1-C100 alkoxy;
• and pentafluorophenyl;
• R103 and R114 are each independently C1-C25 alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms,
• R202 and R203 are each independently selected from the group consisting of H, F, —CN, C1-C100 alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms;
• and C1-C100 alkoxy.