Polymers based on naphthodiones

Abstract

The present invention relates to polymers comprising one or more (repeating) unit(s) of the formula (I), and compounds of formula (III), wherein Y, Y.sup.15, Y.sup.16 and Y.sup.17 are independently of each other a group of formula and their use as IR absorber, organic semiconductor in organic devices, especially in organic photovoltaics and photodiodes, or in a device containing a diode and/or an organic field effect transistor. The polymers and compounds according to the invention can have excellent solubility in organic solvents and excellent film-forming properties. In addition, high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability can be observed, when the polymers and compounds according to the invention are used in organic field effect transistors, organic photovoltaics and photodiodes. ##STR00001##

Claims

1. A polymer, comprising a unit of formula (I): ##STR00182## wherein Y is a group of formula ##STR00183## a is 1, 2, or 3; a′ is 1, 2, or 3; b is 0, 1, 2, or 3; b′ is 0, 1, 2, or 3; c is 0, 1, 2, or 3; c′ is 0, 1, 2, or 3; U.sup.1 is O, S, or NR.sup.1; U.sup.2 is O, S, or NR.sup.2; T.sup.1, T.sup.2, T.sup.3 and T.sup.4 are independently hydrogen, halogen, hydroxyl, cyano, —COOR.sup.103, —OCOR.sup.103, —NR.sup.112COR.sup.103, —CONR.sup.112R.sup.113, —OR.sup.103′, —SR.sup.103′, —SOR.sup.103′, —SO.sub.2R.sup.103′, —NR.sup.112SO.sub.2R.sup.103′, —NR.sup.112R.sup.113, C.sub.1-C.sub.25alkyl, which is optionally substituted by E and/or interrupted by D, C.sub.5-C.sub.12 cycloalkyl, which is optionally substituted one to three times with C.sub.1-C.sub.8 alkyl and/or C.sub.1-C.sub.8 alkoxy; C.sub.7-C.sub.25 arylalkyl, C.sub.6-C.sub.24 aryl, C.sub.6-C.sub.24 aryl which is substituted by G, C.sub.2-C.sub.20 heteroaryl, or C.sub.2-C.sub.20 heteroaryl which is substituted by G; R.sup.1 and R.sup.2 are independently selected from the group consisting of hydrogen, a C.sub.1-C.sub.100alkyl group which is optionally substituted one or more times with C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 alkoxy, halogen, C.sub.5-C.sub.12 cycloalkyl, nitro, cyano, vinyl, allyl, C.sub.6-C.sub.24aryl, C.sub.2-C.sub.20 heteroaryl, a silyl group, or a siloxanyl group; and/or is optionally interrupted by —O—, —S—, —NR.sup.39—, CONR.sup.39—, NR.sup.39CO—, —COO—, —CO— or —OCO—, a C.sub.2-C.sub.100 alkenyl group which is optionally substituted one or more times with C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 alkoxy, halogen, C.sub.5-C.sub.12 cycloalkyl, nitro, cyano, vinyl, allyl, C.sub.6-C.sub.24 aryl, C.sub.2-C.sub.20 heteroaryl, a silyl group, or a siloxanyl group; and/or is optionally interrupted by —O—, —S—, —NR.sup.39—, CONR.sup.39—, NR.sup.39CO—, —COO—, —CO— or —OCO—, a C.sub.3-C.sub.100 alkinyl group which is optionally substituted one or more times with C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 alkoxy, halogen, C.sub.5-C.sub.12 cycloalkyl, nitro, cyano, vinyl, allyl, C.sub.6-C.sub.24 aryl, C.sub.2-C.sub.20 heteroaryl, a silyl group, or a siloxanyl group; and/or is optionally interrupted by —O—, —S—, —NR.sup.39—, CONR.sup.39—, NR.sup.39CO—, —COO—, —CO— or —OCO—, a C.sub.3-C.sub.12 cycloalkyl group which is optionally substituted one or more times with C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 alkoxy, halogen, C.sub.5-C.sub.12 cycloalkyl, nitro, cyano, vinyl, allyl, C.sub.6-C.sub.24 aryl, C.sub.2-C.sub.20 heteroaryl, a silyl group, or a siloxanyl group; and/or is optionally interrupted by —O—, —S—, —NR.sup.39—, CONR.sup.39—, NR.sup.39CO—, —COO—, —CO— or —OCO—, a C.sub.6-C.sub.24 aryl group which is optionally substituted one or more times with C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 alkoxy, halogen, C.sub.5-C.sub.12 cycloalkyl, nitro, cyano, vinyl, allyl, C.sub.6-C.sub.24 aryl, C.sub.2-C.sub.20 heteroaryl, a silyl group, or a siloxanyl group; a C.sub.2-C.sub.20 heteroaryl group which is optionally substituted one or more times with C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 alkoxy, halogen, C.sub.5-C.sub.12 cycloalkyl, nitro, cyano, vinyl, allyl, C.sub.6-C.sub.24 aryl, C.sub.2-C.sub.20 heteroaryl, a silyl group, or a siloxanyl group; a —CO—C.sub.1-C.sub.18 alkyl group, a —CO—C.sub.5-C.sub.12 cycloalkyl group, or —COO—C.sub.1-C.sub.18 alkyl group; R.sup.39 is hydrogen, C.sub.1-C.sub.18 alkyl, C.sub.1-C.sub.18 haloalkyl, C.sub.7-C.sub.25 arylalkyl, or C.sub.1-C.sub.18 alkanoyl, Ar.sup.1, Ar.sup.1′, Ar.sup.2, Ar.sup.2′, Ar.sup.3 and Ar.sup.3′ are independently ##STR00184## ##STR00185## ##STR00186## ##STR00187## ##STR00188##  such as, for example, ##STR00189## ##STR00190##  which optionally is ##STR00191##  wherein X is —O—, —S—, —NR.sup.8—, —Si(R.sup.11)(R.sup.11′)—, —Ge(R.sup.11)(R.sup.11′)—, —C(R.sup.7)(R.sup.7′)—, —C(═O)—, —C(═CR.sup.104R.sup.104′)—, ##STR00192## ##STR00193##  which optionally is ##STR00194##  which optionally is ##STR00195##  wherein X.sup.1 is S, O, NR.sup.107—, —Si(R.sup.117)(R.sup.117′)—, —Ge(R.sup.117)(R.sup.117′)—, —C(R.sup.106)(R.sup.109)—, —C(═O)—, —C(═CR.sup.104R.sup.104′)—, ##STR00196## R.sup.3 and R.sup.3′ are independently hydrogen, halogen, halogenated C.sub.1-C.sub.25 alkyl, cyano, C.sub.1-C.sub.25 alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms; C.sub.7-C.sub.25 arylalkyl, or C.sub.1-C.sub.25 alkoxy; R.sup.4, R.sup.4′, R.sup.5, R.sup.5′, R.sup.6, and R.sup.6′ are independently hydrogen, halogen, halogenated C.sub.1-C.sub.25 alkyl, cyano, C.sub.1-C.sub.25 alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms; C.sub.7-C.sub.25 arylalkyl, or C.sub.1-C.sub.25 alkoxy; R.sup.7, R.sup.7′, R.sup.9 and R.sup.9′ are independently hydrogen, C.sub.1-C.sub.25 alkyl, which is optionally interrupted by one, or more oxygen, or sulphur atoms; or C.sub.7-C.sub.25 arylalkyl, R.sup.8 and R.sup.8′ are independently hydrogen, C.sub.6-C.sub.18 aryl; C.sub.6-C.sub.18 aryl which is substituted by C.sub.1-C.sub.18 alkyl, or C.sub.1-C.sub.18 alkoxy; or C.sub.1-C.sub.25 alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms; or C.sub.7-C.sub.25 arylalkyl, R.sup.11 and R.sup.11′ are independently C.sub.1-C.sub.25 alkyl group, C.sub.7-C.sub.25 arylalkyl, or a phenyl group, which is optionally substituted one to three times with C.sub.1-C.sub.8 alkyl and/or C.sub.1-C.sub.8 alkoxy; R.sup.12 and R.sup.12′ are independently hydrogen, halogen, cyano, C.sub.1-C.sub.25 alkyl, which is optionally interrupted by one, or more oxygen, or sulphur atoms, C.sub.1-C.sub.25 alkoxy, C.sub.7-C.sub.25 arylalkyl, or ##STR00197##  wherein R.sup.13 is a C.sub.1-C.sub.10 alkyl group, or a tri(C.sub.1-C.sub.8 alkyl)silyl group; R.sup.103 and R.sup.103′ are independently C.sub.1-C.sub.100 alkyl, C.sub.1-C.sub.25 alkyl substituted by E and/or interrupted with D, C.sub.7-C.sub.25 arylalkyl, C.sub.6-C.sub.24 aryl, C.sub.6-C.sub.24 aryl which is substituted by G, C.sub.2-C.sub.20 heteroaryl, or C.sub.2-C.sub.20 heteroaryl which is substituted by G, R.sup.104 and R.sup.104′ are independently hydrogen, C.sub.1-C.sub.18 alkyl, cyano, COOR.sup.103, C.sub.6-C.sub.10 aryl, which is optionally substituted by G, or C.sub.2-C.sub.8 heteroaryl, which is optionally substituted by G, R.sup.105, R.sup.105′, R.sup.106 and R.sup.106′ are independently hydrogen, halogen, cyano, C.sub.1-C.sub.25 alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms; C.sub.7-C.sub.25 arylalkyl, or C.sub.1-C.sub.18 alkoxy, R.sup.107 is hydrogen, C.sub.7-C.sub.25 arylalkyl, C.sub.6-C.sub.18 aryl; C.sub.6-C.sub.18 aryl which is substituted by C.sub.1-C.sub.18 alkyl, or C.sub.1-C.sub.18 alkoxy; C.sub.1-C.sub.18 perfluoroalkyl; C.sub.1-C.sub.25 alkyl; which is optionally interrupted by —O—, or —S—; or —COOR.sup.103; R.sup.108 and R.sup.109 are independently H, C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 alkyl which is substituted by E and/or interrupted by D, C.sub.7-C.sub.25 arylalkyl, C.sub.6-C.sub.24 aryl, C.sub.6-C.sub.24 aryl which is substituted by G, C.sub.2-C.sub.20 heteroaryl, C.sub.2-C.sub.20 heteroaryl which is substituted by G, C.sub.2-C.sub.18 alkenyl, C.sub.2-C.sub.18 alkynyl, C.sub.1-C.sub.18 alkoxy, C.sub.1-C.sub.18 alkoxy which is substituted by E and/or interrupted by D, or C.sub.7-C.sub.25 aralkyl, or R.sup.108 and R.sup.109 together form a group of formula ═CR.sup.110R.sup.111, wherein R.sup.110 and R.sup.111 are independently H, C.sub.1-C.sub.18 alkyl, C.sub.1-C.sub.18 alkyl which is substituted by E and/or interrupted by D, C.sub.6-C.sub.24 aryl, C.sub.6-C.sub.24 aryl which is substituted by G, or C.sub.2-C.sub.20 heteroaryl, or C.sub.2-C.sub.20 heteroaryl which is substituted by G, or R.sup.108 and R.sup.109 together form a five or six membered ring, which is optionally substituted by C.sub.1-C.sub.18 alkyl, C.sub.1-C.sub.18 alkyl which is substituted by E and/or interrupted by D, C.sub.6-C.sub.24 aryl, C.sub.6-C.sub.24 aryl which is substituted by G, C.sub.2-C.sub.20 heteroaryl, C.sub.2-C.sub.20 heteroaryl which is substituted by G, C.sub.2-C.sub.18 alkenyl, C.sub.2-C.sub.18 alkynyl, C.sub.1-C.sub.18 alkoxy, C.sub.1-C.sub.18 alkoxy which is substituted by E and/or interrupted by D, or C.sub.7-C.sub.25 aralkyl, D is —CO—, —COO—, —S—, —O—, or —NR.sup.112—, E is C.sub.1-C.sub.8 thioalkoxy, C.sub.1-C.sub.8 alkoxy, CN, —NR.sup.112R.sup.113, —CONR.sup.112R.sup.113, or halogen, G is E, or C.sub.1-C.sub.18 alkyl, and R.sup.112 and R.sup.113 are independently H; C.sub.6-C.sub.18 aryl; C.sub.6-C.sub.18 aryl which is substituted by C.sub.1-C.sub.18 alkyl, or C.sub.1-C.sub.18 alkoxy; C.sub.1-C.sub.18 alkyl; or C.sub.1-C.sub.18 alkyl which is interrupted by —O—, R.sup.114 is C.sub.1-C.sub.25 alkyl, which is optionally interrupted by one, or more oxygen, or sulphur atoms, R.sup.115 and R.sup.115′ are independently hydrogen, halogen, cyano, C.sub.1-C.sub.25 alkyl, which is optionally interrupted by one, or more oxygen, or sulphur atoms, C.sub.1-C.sub.25 alkoxy, C.sub.7-C.sub.25 arylalkyl, or ##STR00198##  wherein R.sup.116 is a C.sub.1-C.sub.10 alkyl group, or a tri(C.sub.1-C.sub.8alkyl)silyl group; R.sup.117 and R.sup.117′ are independently C.sub.1-C.sub.25 alkyl group, C.sub.7-C.sub.25 arylalkyl, or a phenyl group, which is optionally substituted one to three times with C.sub.1-C.sub.8 alkyl and/or C.sub.1-C.sub.8 alkoxy; R.sup.118, R.sup.119, R.sup.120 and R.sup.121 are independently hydrogen, halogen, halogenated C.sub.1-C.sub.25 alkyl, cyano, C.sub.1-C.sub.25 alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms; C.sub.7-C.sub.25 arylalkyl, or C.sub.1-C.sub.25 alkoxy; R.sup.122 and R.sup.122′ are independently hydrogen, C.sub.6-C.sub.18 aryl; C.sub.6-C.sub.18 aryl which is substituted by C.sub.1-C.sub.18 alkyl, or C.sub.1-C.sub.18 alkoxy; or C.sub.1-C.sub.25 alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms; or C.sub.7-C.sub.25 arylalkyl.

2. The polymer according to claim 1, comprising a unit of formula (I′): ##STR00199## wherein Y is a group of formula ##STR00200## U.sup.1 is O, S, or NR.sup.1; U.sup.2 is O, S, or NR.sup.2; T.sup.1, T.sup.2, T.sup.3 and T.sup.4 are independently hydrogen, halogen, cyano, —COOR.sup.103, —OCOR.sup.103, —OR.sup.103′, C.sub.1-C.sub.25 alkyl, which is optionally substituted by E and/or interrupted by D, C.sub.6-C.sub.24 aryl, C.sub.6-C.sub.24 aryl which is substituted by G, C.sub.2-C.sub.20 heteroaryl, or C.sub.2-C.sub.20 heteroaryl which is substituted by G; R.sup.1 and R.sup.2 are independently selected from the group consisting of hydrogen, C.sub.1-C.sub.50 alkyl, C.sub.1-C.sub.50 haloalkyl, C.sub.7-C.sub.25 arylalkyl, C.sub.2-C.sub.50 alkenyl, C.sub.2-C.sub.50 haloalkenyl, allyl, C.sub.5-C.sub.12 cycloalkyl, phenyl or naphthyl which is optionally substituted one or more times with C.sub.1-C.sub.12 alkyl or C.sub.1-C.sub.12 alkoxy, —CO—C.sub.1-C.sub.18 alkyl, —CO—C.sub.5-C.sub.12 cycloalkyl, and —COO—C.sub.1-C.sub.18 alkyl; a is 1, 2, or 3; a′ is 1, 2, or 3; and Ar.sup.1, Ar.sup.1′, R.sup.103, R.sup.103′, D, E and G are as defined in claim 1.

3. The polymer according to claim 1, comprising at least one unit of a formula selected from the group consisting of formula (Ia), formula (Ib), formula (Ic), formula (Id), and formula (Ie): ##STR00201## wherein U.sup.1 is O, or NR.sup.1; U.sup.2 is O, or NR.sup.2; T.sup.1, T.sup.2, T.sup.3 and T.sup.4 are independently hydrogen, or C.sub.1-C.sub.25 alkyl; R.sup.1 and R.sup.2 are independently a C.sub.1-C.sub.38 alkyl group; R.sup.3 and R.sup.3′ are independently hydrogen or C.sub.1-C.sub.25 alkyl; and R.sup.8 and R.sup.8′ are independently hydrogen or C.sub.1-C.sub.25 alkyl.

4. The polymer according to claim 1, comprising a unit of formula ##STR00202## wherein A is a repeating unit of formula (I), and —COM.sup.1- is a repeating unit, which is Ar.sup.1, or is a group of formula ##STR00203## s is 1, t is 1, u is 0, or 1, v is 0, or 1, and Ar.sup.14, Ar.sup.15, Ar.sup.16 and Ar.sup.17 are independently a group of formula ##STR00204## wherein one of X.sup.5 and X.sup.6 is N and the other is CR.sup.14, and R.sup.14, R.sup.14′, R.sup.17 and R.sup.17′ are independently H, or a C.sub.1-C.sub.25 alkyl group.

5. The polymer according to claim 4, wherein A is a repeating unit of formula (Ia), (Ib), (Ic), (Id), or (Ie): ##STR00205## wherein U.sup.1 is O, or NR.sup.1; U.sup.2 is O, or NR.sup.2; T.sup.1, T.sup.2, T.sup.3 and T.sup.4 are independently hydrogen, or C.sub.1-C.sub.25 alkyl; R.sup.1 and R.sup.2 are independently a C.sub.1-C.sub.38 alkyl group; R.sup.3 and R.sup.3′ are independently hydrogen or C.sub.1-C.sub.25 alkyl; and R.sup.8 and R.sup.8′ are independently hydrogen or C.sub.1-C.sub.25 alkyl and ##STR00206##  is a group of formula ##STR00207##  where R.sup.3, R.sup.3′, R.sup.17 and R.sup.17′ are independently hydrogen, or C.sub.1-C.sub.25 alkyl, and R.sup.104 and R.sup.104′ are independently hydrogen, cyano or a C.sub.1-C.sub.25 alkyl group.

6. The polymer according to claim 4, which is a polymer of formula ##STR00208## ##STR00209## ##STR00210## ##STR00211## ##STR00212## ##STR00213## ##STR00214## ##STR00215## ##STR00216## wherein n is 4 to 1000, R.sup.1 and R.sup.2 are independently a C.sub.1-C.sub.38 alkyl group, R.sup.3, R.sup.3″ and R.sup.3′ are independently hydrogen, halogen, cyano, C.sub.1-C.sub.25 alkyl or C.sub.1-C.sub.25 alkoxy, R.sup.4 and R.sup.5 are independently hydrogen, or C.sub.1-C.sub.25 alkyl; R.sup.12 and R.sup.12′ are H, or a C.sub.1-C.sub.25 alkyl group; R.sup.7 and R.sup.7′ are independently hydrogen, C.sub.1-C.sub.25 alkyl, which is optionally interrupted by one, or more oxygen, or sulphur atoms; R.sup.14 and R.sup.14′ are independently hydrogen, halogen, cyano, C.sub.1-C.sub.25 alkyl or C.sub.1-C.sub.25 alkoxy, R.sup.17 and R.sup.17′ are independently H, or a C.sub.1-C.sub.25 alkyl group; R.sup.104 and R.sup.104′ are independently hydrogen, cyano, COOR.sup.103, C.sub.1-C.sub.25 alkyl, R.sup.103 is C.sub.1-C.sub.25 alkyl, R.sup.105, R.sup.105′, R.sup.106 and R.sup.106′ are independently hydrogen, halogen, cyano, C.sub.1-C.sub.25 alkyl or C.sub.1-C.sub.25alkoxy, and R.sup.107 is C.sub.1-C.sub.25 alkyl.

7. A compound of formula ##STR00217## wherein Y, Y.sup.15, Y.sup.16 and Y.sup.17 are independently a group of formula ##STR00218## wherein o is 0, or 1, p is 0, or 1, q is 0, or 1; A.sup.1 and A.sup.2 are independently a group of formula ##STR00219## A.sup.3, A.sup.4 and A.sup.5 are independently a group of formula ##STR00220## k is 1, 2, or 3; l is 0, 1, 2, or 3; r is 0, 1, 2, or 3; z is 0, 1, 2, or 3; R.sup.10 is hydrogen, halogen, cyano, C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 alkyl which is substituted one or more times by E and/or interrupted one or more times by D, ##STR00221##  COO—C.sub.1-C.sub.18 alkyl, C.sub.4-C.sub.18 cycloalkyl group, C.sub.4-C.sub.18 cycloalkyl group, which is substituted by G, C.sub.2-C.sub.18 alkenyl, C.sub.2-C.sub.18 alkynyl, C.sub.1-C.sub.18 thioalkoxy, C.sub.1-C.sub.18 alkoxy, C.sub.1-C.sub.18 alkoxy which is substituted by E and/or interrupted by D, C.sub.7-C.sub.25 aralkyl, C.sub.7-C.sub.25 aralkyl, which is substituted by G, or a group of formulae IVa to IVm, ##STR00222## ##STR00223## wherein R.sup.22 to R.sup.26 and R.sup.29 to R.sup.58 represent independently H, halogen, cyano, C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 alkyl which is substituted by E and/or interrupted by D, C.sub.6-C.sub.24 aryl, C.sub.6-C.sub.24 aryl which is substituted by G, C.sub.2-C.sub.20 heteroaryl, C.sub.2-C.sub.20 heteroaryl which is substituted by G, a C.sub.4-C.sub.18 cycloalkyl group, a C.sub.4-C.sub.18 cycloalkyl group, which is substituted by G, C.sub.2-C.sub.18 alkenyl, C.sub.2-C.sub.18 alkynyl, C.sub.1-C.sub.18 alkoxy, C.sub.1-C.sub.18 alkoxy which is substituted by E and/or interrupted by D, C.sub.7-C.sub.25 aralkyl, or C.sub.7-C.sub.25 aralkyl, which is substituted by G, R.sup.27 and R.sup.28 are independently hydrogen, C.sub.1-C.sub.25 alkyl, halogen, cyano or C.sub.7-C.sub.25 aralkyl, or R.sup.27 and R.sup.28 together represent alkylene or alkenylene which are optionally both bonded via oxygen and/or sulfur to a thienyl residue and which optionally both comprise up to 25 carbon atoms, R.sup.59 is hydrogen, C.sub.6-C.sub.18 aryl; C.sub.6-C.sub.18 aryl which is substituted by C.sub.1-C.sub.18 alkyl, or C.sub.1-C.sub.18 alkoxy; or C.sub.1-C.sub.25 alkyl, which is optionally interrupted by one or more oxygen or sulphur atoms; or C.sub.7-C.sub.25 arylalkyl, D is —CO—, —COO—, —S—, —O—, or —NR.sup.112—, E is C.sub.1-C.sub.8 thioalkoxy, C.sub.1-C.sub.8 alkoxy, CN, —NR.sup.112R.sup.113, —CONR.sup.112R.sup.113, or halogen, G is E, or C.sub.1-C.sub.18 alkyl, and R.sup.112 and R.sup.113 are independently H; C.sub.6-C.sub.18 aryl; C.sub.6-C.sub.18 aryl which is substituted by C.sub.1-C.sub.18 alkyl, or C.sub.1-C.sub.18 alkoxy; C.sub.1-C.sub.18 alkyl; or C.sub.1-C.sub.18 alkyl which is interrupted by —O—; R.sup.214 and R.sup.215 are independently hydrogen, C.sub.1-C.sub.18 alkyl, C.sub.6-C.sub.24 aryl, C.sub.2-C.sub.20 heteroaryl, —CN or COOR.sup.216; R.sup.216 is C.sub.1-C.sub.25 alkyl, C.sub.1-C.sub.25 haloalkyl, C.sub.7-C.sub.25 arylalkyl, C.sub.6-C.sub.24 aryl or C.sub.2-C.sub.20 heteroaryl; Ar.sup.4, Ar.sup.5, Ar.sup.6 and Ar.sup.7 are independently Ar.sup.1, and a, b, c, Ar.sup.1, Ar.sup.2, Ar.sup.3, T.sup.1, T.sup.2, T.sup.3, T.sup.4, U.sup.1 and U.sup.2 are as defined in claim 1, with the proviso that, if o is 0, p is 0, q is 0, and U.sup.1 is O and U.sup.2 is O, T.sup.1, T.sup.2, T.sup.3 and T.sup.4 are each hydrogen, halogen, alkyl, or alkoxy; then the sum of a, b and c is equal, or greater than 2; and the further proviso that, if o is 0, p is 0, q is 0, a is 1, b is 0, c is 0, T.sup.1, T.sup.2, T.sup.3 and T.sup.4 are hydrogen, U.sup.1 is O, U.sup.2 is NH and Ar.sup.1 is a group of formula ##STR00224##  then R.sup.10 is different from OCH.sub.3, OC.sub.2H.sub.5, O(CH.sub.2).sub.2CH.sub.3, OCH(CH.sub.3).sub.2 and O(CH.sub.2).sub.3CH.sub.3.

8. The compound according to claim 7, which is a compound of formula ##STR00225## wherein A.sup.1, A.sup.2, A.sup.3, A.sup.4, A.sup.5, T.sup.1, T.sup.2, T.sup.3, T.sup.4, U.sup.1 and U.sup.2 are as defined in claim 7, T.sup.1′, T.sup.2′, T.sup.3′, T.sup.4′, T.sup.1″, T.sup.2″, T.sup.3″, T.sup.4″, T.sup.1*, T.sup.2*, T.sup.3* and T.sup.4* are independently T.sup.1, and U.sup.1′, U.sup.2′, U.sup.1″, U.sup.2″, U.sup.1* and U.sup.2* are independently U.sup.1.

9. An organic semiconductor material, layer or component, comprising the polymer according to claim 1.

10. A semiconductor device, comprising the polymer according to claim 1.

11. The semiconductor device according to claim 10, which is an organic photovoltaic device, a photodiode, or an organic field effect transistor.

12. A process for preparing an organic semiconductor device, the process comprising: applying a solution and/or dispersion of the polymer according to claim 1 in an organic solvent to a suitable substrate and removing the solvent.

13. A process for preparing a device, the process comprising: employing the polymer according to claim 1 as IR absorber, or organic field effect transistor in the device, wherein the device is a PV device or a photodiode.

14. A compound of formula ##STR00226## wherein a, a′, b, b′, c, c′, Y, Ar.sup.1, Ar.sup.1′, Ar.sup.2, Ar.sup.2′, Ar.sup.3 and Ar.sup.3′ are as defined in claim 1, and X.sup.2 and X.sup.2′ are independently halogen, ZnX.sup.12, —SnR.sup.207R.sup.208R.sup.209, wherein R.sup.207, R.sup.208 and R.sup.209 are independently H or C.sub.1-C.sub.6 alkyl, or two of the groups R.sup.207, R.sup.208 and R.sup.209 form a ring and are optionally branched; —SiR.sup.210R.sup.211R.sup.212, wherein R.sup.210, R.sup.211 and R.sup.212 are independently halogen, or C.sub.1-C.sub.6 alkyl; X.sup.12 is a halogen atom; —OS(O).sub.2CF.sub.3, —OS(O).sub.2-aryl, —OS(O).sub.2CH.sub.3, —B(OH).sub.2, —B(OY.sup.1).sub.2, ##STR00227## —BF.sub.4Na, or —BF.sub.4K, wherein Y.sup.1 is independently in each occurrence a C.sub.1-C.sub.10 alkyl group and Y.sup.2 is independently in each occurrence a C.sub.2-C.sub.10 alkylene group and Y.sup.13 and Y.sup.14 are independently hydrogen, or a C.sub.1-C.sub.10 alkyl group.

15. A process for preparing a polymer of formula ##STR00228## the process comprising reacting a dihalogenide of formula X.sup.10-A-X.sup.10 with an equimolar amount of a diboronic acid or diboronate corresponding to formula X.sup.11—COM.sup.1-X.sup.11, or reacting a dihalogenide of formula X.sup.10—COM.sup.1-X.sup.10 with an equimolar amount of a diboronic acid or diboronate corresponding to formula X.sup.11-A-X.sup.11, wherein X.sup.10 is halogen, and X.sup.11 is independently in each occurrence —B(OH).sub.2, —B(OY.sup.1).sub.2, ##STR00229##  wherein Y.sup.1 is independently in each occurrence a C.sub.1-C.sub.10 alkyl group and Y.sup.2 is independently in each occurrence a C.sub.2-C.sub.10 alkylene group and Y.sup.13 and Y.sup.14 are independently hydrogen, or a C.sub.1-C.sub.10 alkyl group, in a solvent and in the presence of a catalyst; or reacting a dihalogenide of formula X.sup.10-A-X.sup.10 with an equimolar amount of an organo tin compound corresponding to formula ##STR00230##  or reacting a dihalogenide of formula ##STR00231##  with an equimolar amount of an organo tin compound corresponding to formula X.sup.11′-A-X.sup.11′, wherein X.sup.11′ is independently in each occurrence —SnR.sup.207R.sup.208R.sup.209, wherein R.sup.207, R.sup.208 and R.sup.209 are independently H or C.sub.1-C.sub.6 alkyl, or two of the groups R.sup.207, R.sup.208 and R.sup.209 form a ring and are optionally branched, A and COM.sup.1 are as defined in claim 4 and n is in a range of 4 to 1000.

16. A polymer comprising a unit of formula ##STR00232## wherein A.sup.1′ and A.sup.2′ are independently a group of formula ##STR00233##  wherein a, b, c, p, q, Ar.sup.1, Ar.sup.2, Ar.sup.3, Y, Y.sup.15, Y.sup.16, Y.sup.17, A.sup.3, A.sup.4 and A.sup.5 are as defined in claim 7.

Description

EXAMPLES

Example 1

Synthesis of Compound 3

a) 1,5-Bis(α-hydroxyphenylacetylamino)naphthalene (1)

(1) ##STR00157##

(2) A mixture of 1,5-diaminonaphthalene (1.58 g, 10 mmol) and DL-mandelic acid (4.56 g, 30 mmol) in chlorobenzene (40 ml) is heated at 135° C. for 21 hours. On cooling to room temperature, the precipitate is filtered, washed with ethanol and dried in vacuo to yield the product (2.27 g, yield: 55%). NMR (1H, 300 MHz, DMSO): δ ppm 10.10 (s, 2H), 7.74 (d, J=8.4 Hz, 2H), 7.59-7.61 (m, 6H), 7.48 (t, J=8.1 Hz, 2H), 7.40 (t, J=7.2 Hz, 4H), 7.34 (t, J=7.2 Hz, 2H), 6.56 (d, t=4.5 Hz, 2H), 5.27 (d, t=4.5 Hz, 2H).

b) 3,8-Diphenyl-2,7-dioxo-1,2,3,6,7,8-hexahydronaphtho[1,2-b:5,6-b′]dipyrrole (2)

(3) ##STR00158##

(4) 1,5-Bis(a-hydroxyphenylacetylamino)naphthalene (2.27 g, 5.5 mmol) is added to sulfuric acid (20 ml). After stirring at room temperature for 20 hours, the mixture is poured into ice water. The precipitate is filtered, washed with water and dried to yield the product (1.98 g, yield: 92%). NMR (1H, 300 MHz, DMSO): δ ppm 11.26-11.54 (m, 2H), 7.82-7.86 (m, 2H), 7.31-7.62 (m, 8H), 7.18-7.31 (m, 4H), 4.94-5.0 (m, 2H).

c) 3,8-Diphenyl-2,7-dioxo-1,2,6,7-tetrahydronaphtho[1,2-b:5,6-b′]dipyrrole (3)

(5) ##STR00159##

(6) An aqueous sodium hydroxide solution (1.84 ml, 5 N) is dropwisely added to a suspension of 3,8-diphenyl-2,7-dioxo-1,2,3,6,7,8-hexahydronaphtho[1,2-b:5,6-b′]-dipyrrole (1.98 g, 5.06 mmol) in ethanol (16 ml). Then potassium persulfate (3.68 g, 13.63 mmol) in water (12 ml) is added. The resulting mixture is heated at reflux for 3 hours. The precipitate in the mixture is filtered, washed with water and ethanol, and dried to yield the product (1.75 g, yield: 89%). NMR (1H, 500 MHz, DMSO): δ ppm 10.41 (s, 2H), 7.84 (d, J=6 Hz, 2H), 7.51 (t, J=6 Hz, 4H), 7.44 (t, J=8 Hz, 4H), 7.34 (d, J=7.5 Hz, 2H). UV/Vis (DMF, λ.sub.max): 557 nm.

Example 2

Synthesis of Compound 6

a) 1,4-Bis(α-hydroxy(4-bromophenyl)acetylamino)naphthalene (4)

(7) ##STR00160##

(8) A mixture of 1,5-diaminonaphthalene (1.582 g, 10 mmol) and 4-bromo-mandelic acid (6.93 g, 30 mmol) in chlorobenzene (40 ml) is heated at 135° C. for 21 hours. On cooling to room temperature, the precipitate is filtered, washed with ethanol and dried in vacuo to yield the crude product (3.56 g, yield: 61%). The crude product is suspended in chlorobenzene (20 ml), heated to 135° C. stirring for 20 minutes, and is then cooled to room temperature. The precipitated product is filtered off and washed with methanol. The product is dried in air giving a white solid (2.82 g, yield: 48%). NMR (1H, 300 MHz, DMSO): δ ppm 10.13 (s, 2H), 7.74 (d, J=8.1 Hz, 2H), 7.60 (d, J=8.4 Hz, 4H), 7.55 (d, J=8.4 Hz, 4H), 7.49 (t, J=8.0 Hz, 2H), 6.67 (d, J=4.8 Hz, 2H), 5.27 (d, J=4.5 Hz, 2H).

b) 3,8-Di(4-bromophenyl)-2,7-dioxo-1,2,3,6,7,8-hexahydronaphtho[1,2-b:5,6-b′]dipyrrole (5)

(9) ##STR00161##

(10) 1,4-Bis(α-hydroxy(4-bromophenyl)acetylamino)naphthalene (3.56 g, 6.1 mmol) is added to sulfuric acid (20 ml). After stirring at room temperature for 18 hours, the mixture is poured into ice water. The precipitate is filtered, washed with water and dried to yield the product (3.16 g, yield: 95%). NMR (1H, 300 MHz, DMSO): δ ppm 11.27-11.58 (m, 2H), 7.74-7.88 (m, 2H), 7.55-7.57 (m, 6H), 7.15-7.29 (m, 4H), 5.0 (m, 2H).

c) 3,8-Di(4-bromophenyl)-2,7-dioxo-1,2,6,7-tetrahydronaphtho[1,2-b:5,6-b′]dipyrrole (6) (=I-10)

(11) ##STR00162##

(12) An aqueous sodium hydroxide solution (2.11 ml, 5 N) is dropwisely added to a suspension of 3,8-di(4-bromophenyl)-2,7-dioxo-1,2,3,6,7,8-hexahydronaphtho[1,2-b:5,6-b′]dipyrrole (3.16 g, 5.8 mmol) in ethanol (18 ml). Then potassium persulfate (4.22 g, 15.7 mmol) in water (14 ml) is added. The resulting mixture is heated at reflux for 3 hours. The precipitate in the mixture is filtered, washed with water and ethanol, and dried to yield the product (2.88 g, yield: 91%). Microanalysis found C, 58.01%; H, 2.98%, N, 9.89% (C, 57.17%, H, 2.58%, N, 5.13%). UV/Vis (DMF, λ.sub.max): 567 nm.

Example 3

Synthesis of Compound 7

3,8-Bis(4-bromophenyl)naphtho[1,2-b:5,6-b′]difuran-2,7-dione (7)

(13) ##STR00163##

(14) Using a Dean-Stark apparatus, 1,5-dihydroxynaphthalene (0.8 g, 5 mmol), and 4-bromo-mandelic acid (2.31 g, 10 mmol) are dissolved in 1,2,4-trichlorobenzene (10 ml). The reaction mixture is stirred for 4 hours at 200° C. allowing formed water to distil off, before it is cooled to room temperature. Then nitrobenzene (0.67 g, 5 mmol) is added. The mixture is stirred for another half an hour at 200° C. and allowed to cool. A precipitate is formed, which is filtered off, and washed with methanol. The crude product is dissolved in 1,2,4-trichlorobenzene at 200° C., precipitated at room temperature, and digested in hot acetic acid. The product obtained is refluxed in methanol giving a deep purple solid (1.69 g, yield: 62%). Microanalysis found C, 56.93%, H, 2.59% (C, 56.97%; H, 2.21%). UV/Vis (DMF, λ.sub.max): 560 nm.

Example 4

Synthesis of Compound 9

a) 6-Hydroxy-2-oxo-3-phenyl-2,3-dihydronaphtho[1,2-b]furan (8)

(15) ##STR00164##

(16) Using a Dean-Stark apparatus, 1,5-dihydroxynaphthalene (1.6 g, 10 mmol), and DL-mandelic acid (1.5 g, 10 mmol) are dissolved in 1,2,4-trichlorobenzene (15 ml). The reaction mixture is stirred for 1.5 hours at 200° C. During the heating, nitrogen gas is used in order to remove water and to prevent contact with air. The mixture is allowed to cool to room temperature. A precipitate is formed, which is filtered off, washed with a small amount of toluene and hexane, respectively. The crude product is suspended in 1,2,4-trichlorobenzene, heated to 200° C. to dissolve, and is then cooled to room temperature. The precipitated product is filtered off and washed with toluene. The product is dried in air. The dried product is dissolved in DMF and precipitated by adding water. The product is dried in air giving a white solid (1.02 g, yield: 37%). NMR (1H, 300 MHz, DMSO): δ ppm 10.46 (s, 1H), 7.98 (d, J=8.4 Hz, 2H), 7.48 (d, J=8.1 Hz, 1H), 7.45 (s, 1H), 7.41 (s, 1H), 7.37 (d, J=7.5 Hz, 2H), 7.25 (d, J=8.1 Hz, 3H), 5.57 (s, 1H). Microanalysis found C, 79.19%; H, 3.70% (C, 80.0%; H, 3.6%).

b) 3-Phenyl-8-(3,4-dimethoxy-phenyl)naphtho[1,2-b:5,6-b′]difuran-2,7-dione (9)

(17) ##STR00165##

(18) Using a Dean-Stark apparatus, 6-hydroxy-2-oxo-3-phenyl-2,3-dihydronaphtho[1,2-b]furan (1.02 g, 3.7 mmol) and 3,4-dimethoxy-mandelic acid (1.13 g, 7.4 mmol) are dissolved in 1,2,4-trichlorobenzene (15 ml). The reaction mixture is stirred for 4 hours at 200° C. allowing formed water to evaporate and then it is cooled to room temperature. Nitrobenzene (0.91 g, 7.4 mmol) is added and the mixture is stirred for another hour at 200° C. After cooling to room temperature, 40 ml methanol are added. A precipitate is formed, which is filtered off, and washed with methanol. The crude product is dissolved in 1,2,4-trichlorobenzene at 200° C., precipitated at room temperature, and digested in hot acetic acid. The product obtained is refluxed in methanol, giving a dark solid (0.63 g, yield: 38%). Microanalysis found C, 74.01%; H, 3.90% (C, 74.66%, H, 4.03%). UV/Vis (DCM, λ.sub.max): 572 nm. ∈ (572)/L mol.sup.−1 cm.sup.−1: 39222.

Example 5

Synthesis of Compound 10

3,8-Bis(3,4-dimethoxyphenyl)naphtho[1,2-b:5,6-b′]difuran-2,7-dione (10)

(19) ##STR00166##

(20) Using a Dean-Stark apparatus, 1,5-dihydroxynaphthalene (0.8 g, 5 mmol) and 3,4-dimethoxy-mandelic acid (2.12 g, 10 mmol) are dissolved in 1,2,4-trichlorobenzene (10 ml). The reaction mixture is stirred for 4 hours at 200° C. allowing formed water to distil off, before it is cooled to room temperature again. Nitrobenzene (1.23 g, 10 mmol) is added and the mixture is stirred for another hour at 200° C. After cooling to room temperature, 50 ml methanol are added. A precipitate is formed, which is filtered off, and washed with methanol. The crude product is dissolved in 1,2,4-trichlorobenzene at 200° C., precipitated at room temperature, and digested in hot acetic acid. The product obtained is refluxed in methanol giving a dark solid (1.07 g, yield: 42%). Microanalysis found C, 70.31%; H, 4.37% (C, 70.58%; H, 4.37%). UV/Vis (DCM, λ.sub.max): 635 nm. ∈ (635)/L mol.sup.−1 cm.sup.−1: 102626.

Example 6

Synthesis of Compound 11

3,8-Bis(3-bromo-4,5-dimethoxyphenyl)naphtho[1,2-b:5,6-b′]difuran-2,7-dione (11)

(21) ##STR00167##

(22) Using a Dean-Stark apparatus, 1,5-dihydroxynaphthalene (0.8 g, 5 mmol) and 3-bromo-4,5-dimethoxy-mandelic acid (2.92 g, 10 mmol) are dissolved in 1,2,4-trichlorobenzene (10 ml). The reaction mixture is stirred for 4 hours at 200° C. allowing formed water to distil off, before it is cooled to room temperature. Nitrobenzene (1.23 g, 10 mmol) is added and the mixture is stirred for another hour at 200° C. After cooling to room temperature, 50 ml methanol are added. A precipitate is formed, which is filtered off, and washed with methanol. The crude product is dissolved in 1,2,4-trichlorobenzene at 200° C., precipitated at room temperature, and digested in hot acetic acid. The product obtained is refluxed in methanol giving a dark solid (1.57 g, yield: 47%). Microanalysis found C, 52.01%; H, 3.98% (C, 53.92%; H, 3.02%). UV/Vis (DCM, λ.sub.max): 588 nm. ∈ (588)/L mol.sup.−1 cm.sup.−1: 26208.

Example 7

Polymer P-15

(23) ##STR00168##

(24) In a Schlenk flask, 3,8-bis(3-bromo-4,5-dimethoxyphenyl)naphtho[1,2-b:5,6-b′]-difuran-2,7-dione (200.0 mg, 0.30 mmol), 2,5-bis(tributylstannyl)thiophene (198.8 mg, 0.30 mmol) and tetrakis(triphenylphosphine)palladium(0) (17.3 mg, 0.015 mmol), are dissolved in dry DMF (10 ml). Then the mixture is heated and kept at 90° C. under nitrogen for 18 hours. After cooling to room temperature, methanol is added and a precipitate is formed. The precipitate is collected by filtration. Then the product is purified upon Soxhlet extraction with methanol and hexane. A dark solid is obtained. (123 mg, yield: 45%). UV/Vis (1,2,4-trichlorobenzene, λ.sub.max of red shifted absorption band): 644 nm. Molecular weight: 4000 Da.

Example 8

Polymer P-16

(25) ##STR00169##

(26) In a Schlenk flask, 3,8-bis(3-bromo-4,5-dimethoxyphenyl)naphtho[1,2-b:5,6-b′]difuran-2,7-dione (200.0 mg, 0.30 mmol), 2,2′-(9,9-dihexyl-9H-fluorene-2,7-diyl)-bis(4,4-5,5-tetramethyl-1,3,2-dioxaborolane) (176 mg, 0.3 mmol) and tetrakis-(triphenyl-phosphine)palladium(0) (17.3 mg, 0.015 mmol) are dissolved in dry toluene (15 ml) under nitrogen. The reaction is degassed and heated to 50° C. A degassed solution of potassium carbonate (137.8 mg, 1.3 mmol) in water (5 ml) is added. The mixture is stirred at 90° C. for 24 hours. After cooling to room temperature, the dark solution is diluted with DCM, washed three times with water and once with brine. Then the organic layer is dried over anhydrous magnesium sulfate and the solvent is removed by reduced pressure. After that, the crude product is dissolved in a minimal amount of DCM and precipitated in methanol. The product is obtained as a dark solid (43.6 mg, yield: 17%). UV/Vis (DCM, λ.sub.max of red shifted absorption band): 618 nm. Molecular weight: 2100 Da.

Example 9

Synthesis of Compound 12 (=I-10)

(27) ##STR00170##

(28) 500 mg of compound 6 are dissolved in 10 ml of dry dimethylformamide. Then 2.2 equivalents of K.sub.2CO.sub.3 are added, followed by 2.2 equivalents of ethylhexylbromide [18908-66-2]. The reaction mixture is then heated for 21 h at 90° C. The mixture is poured on water and the product is extracted with methylenechloride. The organic phase is dried and evaporated. The product is then purified by column chromatography over silica gel to give compound 12.

Example 10

Synthesis of Polymer P-17

(29) ##STR00171##

(30) The polymer P-17 is obtained according to example 7 starting from compounds 12 and 2,5-bis-trimethylstannyl-thiophene [86134-26-1] in a 1:1 ratio.

Example 11

Synthesis of Compound 13 (I-1)

(31) ##STR00172##

(32) 3,8-Di(4-bromophenyl)-2,7-dioxo-1,2,6,7-tetrahydronaphtho[1,2-b:5,6-b′]dipyrrole (1.5 g, 2.75 mmol) is dissolved in anhydrous dimethylformamide (40 ml) and then potassium carbonate (2.66 g, 19.25 mmol) and 1-iodo-2-octyldodecane (4.49 g, 10.98 mmol) are added. After stirring for 12 hours at 50° C., the mixture is poured into water and extracted with DCM. The organic layer is washed with brine and dried over anhydrous MgSO.sub.4. On removal of the solvent, the crude solid product is obtained. Then the crude product is dissolved in a minimal amount of DCM and precipitated in methanol. The crude product is obtained as a dark solid (1.46 g, yield: 48%). The crude product is purified by column chromatography over silica gel with hexane:DCM=1:2 as eluent to yield the product 13 (0.55 g, 18%). .sup.1H NMR (300 MHz, DMSO): δ ppm 7.65 (d, J=8.7 Hz, 4 H), 7.60 (d, J=8.7 Hz, 4 H), 7.40 (d, J=9.6 Hz, 2H), 7.15 (d, J=9.6 Hz, 2H), 4.07 (d, J=7.2 Hz, 4 H), 1.93 (s, 2H), 1.15-1.35 (br, 64 H), 0.87-0.91 (t, 12 H). Microanalysis found C, 72.05%; H, 4.68%, N, 2.68% (C, 71.59%, H, 4.56%, N, 2.53%). UV/Vis (DCM): 571 nm. ∈ (571)/L mol.sup.−1 cm.sup.−1: 4.9*10.sup.4.

Example 12

Synthesis of Polymer P-18

(33) ##STR00173##

(34) In a Schlenk flask, 3,8-di(4-bromophenyl)-1.6-bis-(2-octyl-dodecyl)-2,7-dioxo-1,2,6,7-tetrahydronaphtho[1,2-b:5,6-b′]dipyrrole (200.0 mg, 0.18), 2,5-bis(tributylstannyl)thiophene (119.0 mg, 0.18 mmol) and tetrakis(triphenylphosphine)palladium(0) (10.4 mg, 0.009 mmol) are dissolved in dry DMF (10 ml). Then the mixture is heated and kept under nitrogen at 90° C. for 18 hours. After cooling to room temperature, methanol is added and a precipitate is formed. The precipitate is collected by filtration. Then the product is purified upon Soxhlet extraction with methanol and hexane. A dark solid is obtained. (96.3 mg, yield: 52%). NMR (.sup.1H, 300 MHz, d.sup.1-CHCl.sub.3): δ ppm 7.82-7.91 (br, 4 H), 7.73-7.79 (br, 4 H), 7.76-7.72 (br, 2 H), 7.38-7.45 (br, 4 H), 4.08-4.12 (br, 2 H), 1.95-2.08 (br, 4 H), 1.19-1.38 (br, 64 H), 0.87-0.99 (br, 12 H). UV/Vis (DCM): 601 nm. Molecular weight: 3.8 kDa.

Example 13

Synthesis of Polymer P-19

(35) ##STR00174##

(36) 400 mg of compound 12 together with an equimolar amount of the diboronic acid pinacol ester [254755-24-3] are dissolved in 10 ml toluene. The solution is degassed with argon. Then 0.05 equivalents Pd(PPh.sub.3).sub.4 are added. In a separate flask 3 equivalents of K.sub.2CO.sub.3 are dissolved in water and degassed with argon. The first solution is heated to 80° C. and then the second solution is added. The reaction mixture is then heated to reflux over night to give polymer P-19.

Example 14

Synthesis of Polymer P-20

(37) ##STR00175##

(38) In a Schlenk flask, 3,8-di(4-bromophenyl)-1.6-bis-(2-octyl-dodecyl)-2,7-dioxo-1,2,6,7-tetrahydronaphtho[1,2-b:5,6-b′]dipyrrole (200.0 mg, 0.18 mmol), 2,2′-(9,9-dihexyl-9H-fluorene-2,7-diyl)-bis(4,4-5,5-tetramethyl-1,3,2-dioxaborolane) (105.6 mg, 0.18 mmol) and tetrakis-(triphenyl-phosphine)palladium(0) (10.4 mg, 0.009 mmol) are dissolved in dry toluene (15 ml) under nitrogen. The reaction is degassed and heated to 50° C. A degassed solution of potassium carbonate (87.1 mg, 0.63 mmol) in water (5 ml) is added. The mixture is stirred at 90° C. for 24 hours. After cooling to room temperature, the dark solution is diluted with dichloromethane (DCM), washed three times with water and once with brine. Then the organic layer is dried over anhydrous magnesium sulfate and the solvent is removed by reduced pressure. After that, the crude product is dissolved in a minimal amount of DCM and precipitated in methanol. The product is obtained as a dark solid (173 mg, yield: 75%). NMR (.sup.1H, 300 MHz, d.sub.1-CHCl.sub.3): δ ppm 7.93-7.96 (br, 4 H), 7.67-7.83 (br, 4 H), 7.93-7.96 (br, 6 H), 7.64-7.67 (br, 4 H), 7.43-7.50 (br, 2 H), 7.18-7.20 (br, 2 H), 3.73-3.76 (m, 2 H), 1.95-2.08 (br, 4 H), 1.56 (s, 4 H), 1.15-1.28 (br, 80 H), 0.65-0.91 (br, 18 H). UV/Vis (DCM): 603 nm. Molecular weight: 11.0 kDa.

Example 15

Synthesis of Polymer P-21

(39) ##STR00176##

(40) In a Schlenk flask 3,8-di(4-bromophenyl)-1.6-bis-2-octyldodecyl-2,7-dioxo-1,2,6,7-tetrahydro-naphtho[1,2-b:5,6-b′]dipyrrole 13 (200.0 mg, 0.18), (4,8-bis(2-ethylhexyloxy)benzo[1,2-b:4,5-b]dithiophene-2,6-diyl)bis(trimethylstannane) (139.5 mg, 0.18 mmol) and tetrakis(triphenylphosphine)palladium(0) (8.2 mg, 0.007 mmol) are dissolved in dry toluene (10 ml). Then the mixture is heated and kept under nitrogen at 100° C. for 18 hours. After cooling to room temperature, methanol is added and a precipitate is formed. The precipitate is collected by filtration. Then the product is purified upon Soxhlet extraction with methanol and hexane. A dark solid is obtained (148.5 mg, yield: 58%). UV/Vis (DCM): 659 nm. UV/Vis (thin film): 684 nm. ∈ (659)/L mol.sup.−1 cm.sup.−1: 4.5*10.sup.4. Molecular weight: 21.6 kDa.

Example 16

Synthesis of Polymer P-22

(41) ##STR00177##

(42) In a Schlenk flask 3,8-di(4-bromophenyl)-1.6-bis-2-octyldodecyl-2,7-dioxo-1,2,6,7-tetrahydro-naphtho[1,2-b:5,6-b′]dipyrrole 13 (200.0 mg, 0.18 mmol), 2,2-(9,9-dioctyl-9H-fluoren-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (105.5 mg, 0.18 mmol) and tetrakis(triphenyl-phosphine)palladium(0) (8.2 mg, 0.007 mmol) are dissolved in dry toluene (10 ml) under nitrogen. The reaction is degassed and heated to 50° C. A degassed solution of potassium carbonate (82.68 mg, 0.78 mmol) in water (3 ml) is added. The mixture is stirred at 90° C. for 24 hours. After cooling to room temperature, the dark solution is diluted with DCM, washed three times with water and once with brine. Then the organic layer is dried over anhydrous magnesium sulfate and the solvent is removed at reduced pressure. After that the crude product is dissolved in a minimal amount of DCM and precipitated in methanol. The product is obtained as a dark solid (43.6 mg, yield: 17%). UV/Vis (DCM): 612 nm. UV/Vis (thin film): 639 nm. ∈ (612)/L mol.sup.−1 cm.sup.−1: 8.8*10.sup.4. Molecular weight: 25.6 kDa.

Example 17

Synthesis of Compound 14

3,8-Di(4-bromophenyl)-1.6-bis-dodecyl-2,7-dioxo-1,2,6,7-tetrahydro-naphtho[1,2-b:5,6-b′]dipyrrole

(43) ##STR00178##

(44) 3,8-Di(4-bromophenyl)-2,7-dioxo-1,2,6,7-tetrahydronaphtho[1,2-b:5,6-b′]dipyrrole (1.5 g, 2.75 mmol) is dissolved in anhydrous dimethylformamide (40 ml), and then potassium carbonate (2.66 g, 19.25 mmol) and n-dodecyl iodide (3.39 g, 10.98 mmol) are added. After stirring for 12 hours at 50° C., the mixture is poured into water and extracted with DCM. The organic layer is washed with brine and dried over anhydrous MgSO.sub.4. On removal of the solvent, the crude solid product is obtained. Then the crude product is dissolved in a minimal amount of DCM and precipitated in methanol. The crude product is obtained as a dark solid (1.41 g, yield: 52%). The crude product is purified by column chromatography over silica gel with hexane:DCM=1:2 as eluent to yield the product (0.54 g, 20%). .sup.1H NMR (300 MHz, DMSO): δ ppm 7.65 (d, J=8.7 Hz, 4 H), 7.60 (d, J=8.7 Hz, 4 H), 7.40 (d, J=9.6 Hz, 2H), 7.15 (d, J=9.6 Hz, 2H), 4.07 (t, 4H), 1.77 (m, 4H), 1.15-1.35 (br, 36 H), 0.87-0.91 (t, 6 H). Microanalysis found C, 67.95%; H, 7.12%, N, 3.19% (C, 68.02%, H, 7.08%, N, 3.17%). UV/Vis (DCM): 571 nm. ∈ (571)/L mol.sup.−1 cm.sup.−1: 4.6*10.sup.4.

Example 18

Synthesis of Polymer P-23

(45) ##STR00179##

(46) In a Schlenk flask 3,8-di(4-bromophenyl)-1.6-bis-dodecyl-2,7-dioxo-1,2,6,7-tetrahydro-naphtho[1,2-b:5,6-b′]dipyrrole 14 (200.0 mg, 0.23), (4,8-bis(2-ethylhexyloxy)benzo[1,2-b:4,5-b]dithiophene-2,6-diyl)bis(trimethylstannane) (174.9 mg, 0.23 mmol) and tetrakis(triphenylphosphine)palladium(0) (10.4 mg, 0.009 mmol) are dissolved in dry toluene (10 ml). Then the mixture is heated and kept under nitrogen at 100° C. for 18 hours. After cooling to room temperature methanol is added and a precipitate is formed. The precipitate is collected by filtration. Then the product is purified upon Soxhlet extraction with methanol and hexane. A dark solid is obtained (173.5 mg, yield: 63%). UV/Vis (DCM): 666 nm. UV/Vis (thin film): 696 nm. ∈ (666)/L mol.sup.−1 cm.sup.−1: 4.3*10.sup.4. Molecular weight: 14.2 kDa.

Example 19

Synthesis of Polymer P-24

(47) ##STR00180##

(48) In a Schlenk flask, 3,8-di(4-bromophenyl)-1.6-bis-dodecyl-2,7-dioxo-1,2,6,7-tetrahydro-naphtho[1,2-b:5,6-b′]dipyrrole 14 (200.0 mg, 0.23 mmol), 2,2-(9,9-dioctyl-9H-fluoren-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (132.8 mg, 0.23 mmol) and tetrakis(triphenyl-phosphine)palladium(0) (10.4 mg, 0.009 mmol) are dissolved in dry toluene (10 ml) under nitrogen. The reaction is degassed and heated to 50° C. A degassed solution of potassium carbonate (105.6 mg, 1.0 mmol) in water (3.5 ml) is added. The mixture is stirred at 90° C. for 24 hours. After cooling to room temperature, the dark solution is diluted with DCM, washed three times with water and once with brine. Then the organic layer is dried over anhydrous magnesium sulfate and the solvent is removed at reduced pressure. After that the crude product is dissolved in a minimal amount of DCM and precipitated in methanol. The product is obtained as a dark solid (128.6 mg, yield: 49%). UV/Vis (DCM): 603 nm. UV/Vis (thin film): 624 nm. ∈ (603)/L mol.sup.−1 cm.sup.−1: 8.6*10.sup.4. Molecular weight: 14.8 kDa

Example 20

Synthesis of Polymer P-25

(49) ##STR00181##

(50) In a Schlenk flask 3,8-di(4-bromophenyl)-1.6-bis-dodecyl-2,7-dioxo-1,2,6,7-tetrahydro-naphtho[1,2-b:5,6-b′]dipyrrole 14 (200.0 mg, 0.23), 2,5-bis(trimethylstannane)thiophene (92.8 mg, 0.23 mmol) and tetrakis-(triphenyl-phosphine)palladium(0) (10.4 mg, 0.009 mmol) are dissolved in dry DMF (10 ml). Then the mixture is heated and kept under nitrogen at 100° C. for 18 hours. After cooling to room temperature, methanol is added and a precipitate is formed. The precipitate is collected by filtration. Then the product is purified upon Soxhlet extraction with methanol and hexane. A dark solid is obtained. (96.3 mg, yield: 52%). UV/Vis (DCM): 615 nm. UV/Vis (thin film): 678 nm. ∈ (615)/L mol.sup.−1 cm.sup.−1: 2.8*10.sup.4. Molecular weight: 14.9 kDa.

Application Example 1

UV/Vis Absorption Spectra

(51) UV/Vis absorption spectra of polymer 20 are recorded on an Agilent 8453 spectrometer. The .sup.maxλ.sub.abs in trichloroethylene (TCE) solution and as film are shown in Table 1. Band Gap (BG) is calculated as onset of absorption spectrum.

(52) TABLE-US-00002 TABLE 1 Polymer Solvent .sup.maxλ.sub.abs [nm] P-20 CHCl═CCl.sub.2 330, 600 P-20 Film 335, 610

Application Example 2

Cyclic Voltammograms (CVs)

(53) CVs of the films are recorded on a Autolab PGSTAT302 potentiostat in acetonitrile containing tetrabutylammonium-tetrafluoroborate (Bu.sub.4NBF.sub.4, 0.1M) as supporting electrolyte at scan rate 100 mV/s. Counter and working electrodes are made of Pt and the reference electrode is Ag/AgCl. Films are drop casted on the Pt disc working electrode. All the potentials are calibrated vs. Ferrocene/Ferrocenium redox couple and HOMO/LUMO values are calculated as follows:
HOMO(CV)=−4.8−E.sup.ox.sub.onsetLUMO(CV)=−4.8−E.sup.red.sub.onset

(54) All values are shown in Table 2.

(55) TABLE-US-00003 TABLE 2 Polymer Onset UV, nm BG, eV HOMO (CV), eV LUMO (CV), eV P-20 738 1.68 −5.4 not determined