Functionnalized benzodithiophene polymers for electronic application

Abstract

The present invention relates to polymers comprising a repeating unit of the formula (I), and their use as organic semiconductor in organic electronic devices, especially in organic photovoltaics and photodiodes, or in a device containing a diode and/or an organic field effect transistor. The polymers 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 according to the invention are used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes. ##STR00001##

Claims

1. A polymer, comprising a repeating unit of the formula ##STR00152## wherein R.sup.1 is hydrogen, C.sub.1-C.sub.100alkyl, or a group of formula SiR.sup.501R.sup.502R.sup.503; R.sup.2 is CN, CF.sub.3, a fluorine atom, or a group of the formula ##STR00153## R.sup.301, R.sup.302 and R.sup.303 are independently of each other C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is substituted by E and/or interrupted by D, C.sub.1-C.sub.100fluoroalkyl, C.sub.3-C.sub.12cycloalkyl, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl group, which is be substituted by G; C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl, C.sub.7-C.sub.25aralkyl, or C.sub.7-C.sub.25aralkyl which is substituted by G; C.sub.2-C.sub.20heteroaryl, or C.sub.2-C.sub.20heteroaryl, which is substituted by G; R.sup.601 and R.sup.602 are independently of each other H, or C.sub.1-C.sub.25alkyl; R.sup.501, R.sup.502 and R.sup.503 are independently of each other C.sub.1-C.sub.8alkyl, C.sub.6-C.sub.24aryl, or C.sub.7-C.sub.12aralkyl; D is CO, COO, S, SO, SO.sub.2, O, NR.sup.65, SiR.sup.70R.sup.71, POR.sup.72, CR.sup.63CR.sup.64, or CC, and E is OR.sup.69, SR.sup.69, NR.sup.65R.sup.66, COR.sup.68, COOR.sup.67, CONR.sup.65R.sup.66, CN, CF.sub.3, or halogen, G is E, C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkyl which is interrupted by O, R.sup.63 and R.sup.64 are independently of each other C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by O; R.sup.65 and R.sup.66 are independently of each other C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by O; or R.sup.65 and R.sup.66 together form a five or six membered ring, R.sup.67 is C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by O, R.sup.68 is H; C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by O, R.sup.69 is C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by O, R.sup.70 and R.sup.71 are independently of each other C.sub.1-C.sub.18alkyl, C.sub.6-C.sub.18aryl, or C.sub.6-C.sub.18aryl, which is substituted by C.sub.1-C.sub.18alkyl, and R.sup.72 is C.sub.1-C.sub.18alkyl, C.sub.6-C.sub.18aryl, or C.sub.6-C.sub.18aryl, which is substituted by C.sub.1-C.sub.18alkyl.

2. The polymer according to claim 1, which is a polymer comprising a repeating unit of the formula ##STR00154## wherein R.sup.1 is hydrogen, or C.sub.1-C.sub.100alkyl, R.sup.301 is C.sub.1-C.sub.18alkyl, phenyl, phenyl, which is substituted by one, or more groups selected from C.sub.1-C.sub.18alkyl, halogen, OR.sup.69, CN, or CF.sub.3; wherein R.sup.69 is C.sub.1-C.sub.18alkyl, or phenyl; R.sup.601 and R.sup.602 are the same and are hydrogen or C.sub.1-C.sub.18alkyl.

3. The polymer according to claim 1, which is a polymer comprising a repeating unit of the formula ##STR00155## wherein R.sup.1 is hydrogen, or C.sub.1-C.sub.100alkyl, and R.sup.601 and R.sup.602 are the same and are hydrogen, or C.sub.1-C.sub.18alkyl.

4. The polymer according to claim 1, wherein the polymer is a polymer of formula ##STR00156## or a polymer, comprising repeating units of the formula ##STR00157## wherein n is in the range of 4 to 1000, A is a repeating unit of formula (I), and COM1- is a repeating unit ##STR00158## wherein k is 0, 1, 2, or 3; 1 is 1, 2, or 3; r is 0, 1, 2, or 3; z is 0, 1, 2, or 3; Ar.sup.4, Ar.sup.5, Ar.sup.6 and Ar.sup.7 are independently of each other a group of formula and ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## 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), ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## 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.108)(R.sup.109), C(O), ##STR00172## R.sup.3 and R.sup.3 are independently of each other hydrogen, halogen, halogenated C.sub.1-C.sub.25alkyl, cyano, C.sub.1-C.sub.25alkyl, which are optionally interrupted by one or more oxygen or sulphur atoms; C.sub.7-C.sub.25arylalkyl, or C.sub.1-C.sub.25alkoxy; R.sup.104 and R.sup.104 are independently of each other hydrogen, cyano, COOR.sup.103, a C.sub.1-C.sub.25alkyl group, or C.sub.6-C.sub.24aryl or C.sub.2-C.sub.20heteroaryl, R.sup.4, R.sup.4, R.sup.5, R.sup.5, R.sup.6, and R.sup.6 are independently of each other hydrogen, halogen, halogenated C.sub.1-C.sub.25alkyl, cyano, C.sub.1-C.sub.25alkyl, which are optionally interrupted by one or more oxygen or sulphur atoms; C.sub.7-C.sub.25arylalkyl, or C.sub.1-C.sub.25alkoxy; R.sup.7, R.sup.7, R.sup.9 and R.sup.9 are independently of each other hydrogen, C.sub.1-C.sub.25alkyl, which are optionally interrupted by one, or more oxygen, or sulphur atoms; or C.sub.7-C.sub.25arylalkyl, R.sup.8 and R.sup.8 are independently of each other hydrogen, C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; or C.sub.1-C.sub.25alkyl, which are optionally interrupted by one or more oxygen or sulphur atoms; or C.sub.7-C.sub.25arylalkyl, R.sup.11 and R.sup.11 are independently of each other C.sub.1-C.sub.25alkyl group, C.sub.7-C.sub.25arylalkyl, or a phenyl group, which are optionally substituted one to three times with C.sub.1-C.sub.8alkyl and/or C.sub.1-C.sub.8alkoxy; R.sup.12 and R.sup.12 are independently of each other hydrogen, halogen, cyano, C.sub.1-C.sub.25alkyl, which are optionally interrupted by one, or more oxygen, or sulphur atoms, C.sub.1-C.sub.25alkoxy, C.sub.2-C.sub.25arylalkyl, or ##STR00173## wherein R.sup.13 is a C.sub.1-C.sub.10alkyl group, or a tri(C.sub.1-C.sub.8alkyl)alkyl group; R.sup.104 and R.sup.104 are independently of each other hydrogen, C.sub.1-C.sub.18alkyl, C.sub.6-C.sub.10aryl, which are 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 of each other hydrogen, halogen, cyano, C.sub.1-C.sub.25alkyl, which are optionally interrupted by one or more oxygen or sulphur atoms; C.sub.7-C.sub.25arylalkyl, or C.sub.1-C.sub.18alkoxy, R.sup.107 is hydrogen, C.sub.7-C.sub.25arylalkyl, C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18perfluoroalkyl; C.sub.1-C.sub.25alkyl; which is optionally interrupted by O, or S; or COOR.sup.103; R.sup.108 and R.sup.109 are independently of each other H, C.sub.1-C.sub.25alkyl, C.sub.1-C.sub.25alkyl which is substituted by E and/or interrupted by D, C.sub.7-C.sub.25arylalkyl, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl which is substituted by G, C.sub.2-C.sub.20heteroaryl, C.sub.2-C.sub.20heteroaryl which is substituted by G, C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl, C.sub.1-C.sub.18alkoxy, C.sub.1-C.sub.18alkoxy which is substituted by E and/or interrupted by D, or C.sub.7-C.sub.25aralkyl, or R.sup.108 and R.sup.109 together form a group of formula CR.sup.100R.sup.111, wherein R.sup.110 and R.sup.111 are independently of each other H, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is substituted by E and/or interrupted by D, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl which is substituted by G, or C.sub.2-C.sub.20heteroaryl, or C.sub.2-C.sub.20heteroaryl which is substituted by G, or R.sup.108 and R.sup.109 together form a five or six membered ring, which optionally can be substituted by C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is substituted by E and/or interrupted by D, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl which is substituted by G, C.sub.2-C.sub.20heteroaryl, C.sub.2-C.sub.20heteroaryl which is substituted by G, C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl, C.sub.1-C.sub.18alkoxy, C.sub.1-C.sub.18alkoxy which is substituted by E and/or interrupted by D, or C.sub.7-C.sub.25aralkyl, D is CO, COO, S, O, or NR.sup.112, E is C.sub.1-C.sub.8thioalkoxy, C.sub.1-C.sub.8alkoxy, CN, NR.sup.112R.sup.113, CONR.sup.112R.sup.113, or halogen, G is E, or C.sub.1-C.sub.18alkyl, and R.sup.112 and R.sup.113 are independently of each other H; C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by O, R.sup.115 and R.sup.115 are independently of each other hydrogen, halogen, cyano, C.sub.1-C.sub.25alkyl, which are optionally interrupted by one, or more oxygen, or sulphur atoms, C.sub.1-C.sub.25alkoxy, C.sub.7-C.sub.25arylalkyl, or ##STR00174## wherein R.sup.116 is a C.sub.1-C.sub.18alkyl group, or a tri(C.sub.1-C.sub.8alkyl)silyl group; R.sup.117 and R.sup.117 are independently of each other C.sub.1-C.sub.25alkyl group, C.sub.7-C.sub.25arylalkyl, or a phenyl group, which are optionally substituted one to three times with C.sub.1-C.sub.8alkyl and/or C.sub.1-C.sub.8alkoxy; R.sup.118, R.sup.119, R.sup.120 and R.sup.121 are independently of each other hydrogen, halogen, halogenated C.sub.1-C.sub.25alkyl, cyano, C.sub.1-C.sub.25alkyl, which are optionally interrupted by one or more oxygen or sulphur atoms; C.sub.7-C.sub.25arylalkyl, or C.sub.1-C.sub.25alkoxy; R.sup.122 and R.sup.122 are independently of each other hydrogen, C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; or C.sub.1-C.sub.25alkyl, which are optionally interrupted by one or more oxygen or sulphur atoms; or C.sub.7-C.sub.25arylalkyl; R.sup.201 is selected from hydrogen, a C.sub.1-C.sub.100alkyl group, COOR.sup.103, a C.sub.1-C.sub.100alkyl group substituted by one or more halogen atoms, hydroxyl groups, nitro groups, CN, or C.sub.6-C.sub.18aryl groups and/or interrupted by O, COO, OCO or S; a C.sub.7-C.sub.25arylalkyl group, a carbamoyl group, a C.sub.5-C.sub.12cycloalkyl group, which are substituted one to three times with C.sub.1-C.sub.100alkyl and/or C.sub.1-C.sub.100alkoxy, a C.sub.6-C.sub.24aryl group, which are optionally substituted one to three times with C.sub.1-C.sub.100alkyl, C.sub.1-C.sub.100thioalkoxy, and/or C.sub.1-C.sub.100alkoxy; and pentafluorophenyl; R.sup.103 and R.sup.114 are independently of each other C.sub.1-C.sub.25alkyl, which are optionally interrupted by one, or more oxygen, or sulphur atoms, R.sup.202 and R.sup.203 may be the same or different and are selected from H, F, CN, C.sub.1-C.sub.100alkyl, which are optionally interrupted by one or more oxygen, or sulphur atoms; and C.sub.1-C.sub.100alkoxy.

5. The polymer according to claim 1, comprising repeating units of the formula ##STR00175## wherein A is a repeating unit of formula (I), and COM.sup.1- is a repeating unit of formula ##STR00176## ##STR00177## ##STR00178## wherein R.sup.3, R.sup.3, R.sup.4 and R.sup.4 are independently of each other hydrogen, or C.sub.1-C.sub.25alkyl; R.sup.8 and R.sup.8 are independently of each other hydrogen, or C.sub.1-C.sub.25alkyl; R.sup.114 is a C.sub.1-C.sub.38alkyl group; R.sup.201 is a C.sub.1-C.sub.38alkyl group; and R.sup.202 and R.sup.203 are independently of each other hydrogen or C.sub.1-C.sub.25alkyl.

6. The polymer according to claim 4, which is a polymer of formula ##STR00179## wherein n is 4 to 1000, A is a repeating unit of formula ##STR00180## wherein R.sup.1 is selected from hydrogen, or C.sub.1-C.sub.25alkyl, R.sup.301 is C.sub.1-C.sub.18alkyl, phenyl, phenyl, which is substituted by one, or more groups selected from C.sub.1-C.sub.18alkyl, halogen, OR.sup.69, CN, or CF.sub.3; wherein R.sup.69 is C.sub.1-C.sub.18alkyl, or phenyl; R.sup.601 and R.sup.602 are hydrogen; and ##STR00181## is a group of formula ##STR00182## ##STR00183## wherein R.sup.3, R.sup.3, R.sup.4 and R.sup.4 are independently of each other hydrogen, or C.sub.1-C.sub.25alkyl; and R.sup.201 is a C.sub.1-C.sub.38alkyl group.

7. The polymer according to claim 5, which is a polymer of the formula ##STR00184## ##STR00185## wherein n is 4 to 1000; R.sup.1 is hydrogen or C.sub.1-C.sub.100alkyl, R.sup.3 and R.sup.3 are independently of each other hydrogen or C.sub.1-C.sub.25alkyl; R.sup.201 is a C.sub.1-C.sub.38alkyl group, R.sup.301 is C.sub.1-C.sub.18alkyl, phenyl, phenyl, which is substituted by one, or more groups selected from C.sub.1-C.sub.18alkyl, halogen, OR.sup.69, CN, or CF.sub.3; wherein R.sup.69 is C.sub.1-C.sub.18alkyl, or phenyl; R.sup.601 and R.sup.602 are independently of each other hydrogen, or C.sub.1-C.sub.25alkyl.

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

9. An electronic device, comprising the polymer according to claim 1.

10. The electronic device according to claim 9, wherein the electronic device is an organic light emitting diode, an organic photovoltaic device, a photodiode, or an organic field effect transistor.

11. A process for the preparation of an electronic device, which process comprises 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.

12. A method comprising incorporating the polymer according to claim 1 into organic light emitting diodes, photovoltaic devices, photodiodes, or organic field effect transistors.

13. A compound of the formula ##STR00186## wherein X.sup.2 and X.sup.2 are independently of each other halogen, ZnX.sup.12, SnR.sup.207R.sup.208R.sup.209, wherein R.sup.207, R.sup.208 and R.sup.209 are identical or different and are H or C.sub.1-C.sub.6alkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or unbranched and X.sup.12 is a halogen atom; SiR.sup.210R.sup.211R.sup.212, wherein R.sup.210, R.sup.211 and R.sup.212 are identical or different and are halogen, or C.sub.1-C.sub.6alkyl; 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, ##STR00187## BF.sub.4Na or BF.sub.4K, wherein Y.sup.1 is independently in each occurrence a C.sub.1-C.sub.10alkyl group and Y.sup.2 is independently in each occurrence a C.sub.2-C.sub.10alkylene group and Y.sup.13 and Y.sup.14 are independently of each other hydrogen, or a C.sub.1-C.sub.10alkyl group; and A is a unit of the formula ##STR00188## wherein R.sup.1 is hydrogen, C.sub.1-C.sub.100alkyl, or a group of formula SiR.sup.501R.sup.502R.sup.503; R.sup.2 is CN, CF.sub.3, a fluorine atom, or a group of the formula ##STR00189## R.sup.301, R.sup.302 and R.sup.303 are independently of each other C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkyl which is substituted by E and/or interrupted by D, C.sub.1-C.sub.100fluoroalkyl, C.sub.3-C.sub.12cycloalkyl, C.sub.6-C.sub.24aryl, C.sub.6-C.sub.24aryl group, which is substituted by G; C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl, C.sub.7-C.sub.25aralkyl, or C.sub.7-C.sub.25aralkyl which is substituted by G; C.sub.2-C.sub.20heteroaryl, or C.sub.2-C.sub.20heteroaryl, which is substituted by G; R.sup.601 and R.sup.602 are independently of each other H, or C.sub.1-C.sub.25alkyl; R.sup.501, R.sup.502 and R.sup.503 are independently of each other C.sub.1-C.sub.8alkyl, C.sub.6-C.sub.24aryl, or C.sub.7-C.sub.12aralkyl; D is CO, COO, S, SO, SO.sub.2, O, NR.sup.65, SiR.sup.70R.sup.71, POR.sup.72, CR.sup.63CR.sup.64, or CC, and E is OR.sup.69, SR.sup.69, NR.sup.65R.sup.66, COR.sup.68, COOR.sup.67, CONR.sup.65R.sup.66, CN, CF.sub.3, or halogen, G is E, C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkyl which is interrupted by O, R.sup.63 and R.sup.64 are independently of each other C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by O; R.sup.65 and R.sup.66 are independently of each other C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by O; or R and R.sup.66 together form a five or six membered ring, R.sup.67 is C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by O, R.sup.68 is H; C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by O, R.sup.69 is C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by O, R.sup.70 and R.sup.71 are independently of each other C.sub.1-C.sub.18alkyl, C.sub.6-C.sub.18aryl, or C.sub.6-C.sub.18aryl, which is substituted by C.sub.1-C.sub.18alkyl, and R.sup.72 is C.sub.1-C.sub.18alkyl, C.sub.6-C.sub.18aryl, or C.sub.6-C.sub.18aryl, which is substituted by C.sub.1-C.sub.18alkyl.

14. A process for the preparation of a polymer of formula ##STR00190## 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 ##STR00191## or reacting a dihalogenide of formula ##STR00192## 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, ##STR00193## wherein Y.sup.1 is independently in each occurrence a C.sub.1-C.sub.10alkyl group and Y.sup.2 is independently in each occurrence a C.sub.2-C.sub.10alkylene group and Y.sup.13 and Y.sup.14 are independently of each other hydrogen, or a C.sub.1-C.sub.10alkyl 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 ##STR00194## or reacting a dihalogenide of formula ##STR00195## 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 identical or different and are H or C.sub.1-C.sub.6alkyl, or two of the groups R.sup.207, R.sup.208 and R.sup.209 form a ring and these groups are optionally branched, A and COM.sup.1 are as defined in claim 4, X.sup.10 is as defined above and n is in the range of 4 to 1000.

Description

EXAMPLES

Example 1

Synthesis of Polymer P-1

(1) ##STR00119##

(2) a) In a 250 mL flask previously flushed with nitrogen and equipped with a condenser and a nitrogen bubbler, is introduced [4-bromo-5-(3-bromo-5-trimethylsilyl-2-thienyl)-2-thienyl]-trimethyl-silane 101 (10.0 g, 21.3 mmol) and tetrahydrofuran (THF, 120 mL). The solution is cooled to 78 C. and n-Butyllithium (2.7 M in heptane, 17.4 mL, 47.0 mmol) is added dropwise. The mixture is stirred 1 h at 78 C. and then 30 minutes at 0 C. After that time the solution is cooled to 78 C. again and iodine (11.92 g, 47.0 mmol) is added in a single portion. The mixture is stirred 30 minutes at 78 C. and then left to warm to room temperature over 2 h. After that time a saturated aqueous solution of sodium thiosulphate (100 ml) is added and the product is extracted with tert-butyl-methyl-ether (TBME) and dichloromethane. The organic layers are then dried over sodium sulphate. The solvent is then evaporated on rotary evaporator. The product can then be recrystallized from ethanol: The crude brown solid is dissolved in hot ethanol and then cooled to 78 C., where a beige solid precipitates. The solid is filtered, washed with cold ethanol and dried at 70 C. under reduced pressure for 4 h. This affords the desired compound as a beige solid (9.2 g, 77% yield).

(3) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =7.23 (2H, s), 0.34 (18H, s); .sup.13C (100.1 MHz, CDCl.sub.3), =145.0 (2C), 141.8 (2C), 139.9 (2C), 85.7 (2C), 0.3 (6C).

(4) ##STR00120##

(5) b) In a 1 liter flask is introduced compound 102 (51.18 g, 91.00 mmol). Dimethyl formamide (450 mL) is added under argon and the solution is degassed with argon. After, methyl-2-nonynoate (33.46 mL, 182.0 mmol) is added under argon at room temperature, followed by tributylamine (45.53 mL, 191.1 mmol) and Pd(OAc).sub.2 (2.043 g, 9.10 mmol). The reaction mixture is then heated to 130 C. for 4 h. After that time the solution was cooled to room temperature and concentrated on rotary evaporator. Water (500 mL), and tert-butyl-methyl ether (TBME, 500 mL) are added. The phases are separated and the water phase is extracted with TBME (300 mL). The combined organic phases are washed with water (500 mL) and brine (400 mL) and dried over sodium sulphate, filtered and the solvent was evaporated on rotary evaporator to give a dark brown oil. The crude oil is purified by flash chromatography (Silica gel, toluene/hexane 1:2) to afford the desired product 103 (orange oil, 15.81 g, 24% yield).

(6) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =7.62 (1H, s), 7.59 (1H, s), 4.05 (3H, s), 3.14 (2H, t, J=8.0 Hz), 1.74 (2H, quint., J=8.0 Hz), 1.49-1.44 (2H, m), 1.39-1.34 (4H, m), 0.92 (3H, t, J=7.0 Hz), 0.43 (9H, s), 0.41 (9H, s).

(7) ##STR00121##

(8) c) In a 50 mL round bottom flask, equipped with a condenser is introduced compound 103 (2.38 g, 5.00 mmol). The flask is flushed with argon and dry and degassed tetrahydrofuran (THF, 14 mL) is added. Tetrabutylammonium fluoride trihydrate (TBAF, 3.47 g, 11.0 mmmol) is then added slowly added at room temperature as a solution in THF (11 mL). The resulting solution is then stirred overnight at room temperature. After that time tert-butyl-methyl-ether (TBME, 25 mL) is added and the organic phase is washed with water (250 mL) and brine (40 mL). The aqueous phases are then extracted with TBME (30 mL). The combined organic fractions are then dried over sodium sulphate, filtered and the solvent is evaporated on rotary evaporator to obtain a brown oil. The crude oil is then purified by flash column chromatography (Silica gel, toluene/cyclohexane 1:2, then 1:1) to obtain compound 104 (yellow oil, 1.455 g, 87% yield).

(9) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =7.54 (1H, d, J=5.5 Hz), 7.53 (1H, d, J=5.5 Hz), 7.44 (1H, d, J=5.5 Hz), 7.42 (1H, d, J=5.5 Hz), 4.04 (3H, s), 3.13 (2H, t, J=8.0 Hz), 1.78-1.70 (2H, m), 1.49-1.42 (2H, m), 1.37-1.32 (4H, m), 0.91 (3H, t, J=7.0 Hz); .sup.13C (100.1 MHz, CDCl.sub.3), =169.5, 136.7, 135.6, 135.0, 134.7, 132.0, 124.7, 124.6, 124.4, 123.8, 123.7, 52.1, 31.9, 31.6, 31.6 29.6, 22.6, 14.0. GC/MS: (CI pos.): 333.14 (MH.sup.+).

(10) ##STR00122##

(11) d) In a 3-neck flask equipped with a condenser and an addition funnel are introduced, under nitrogen, compound 104 (2.493 g, 7.50 mmol) and tetrahydrofuran (THF, 25 mL) followed by isopropoxypinacolborane (3.070 g, 16.50 mmol). The resulting solution is then cooled to 78 C. and a previously prepared lithium diisopropylamide solution (LDA, 15.37 mmol in 15 mL THF) is added dropwise. The reaction mixture is left to stir 1 h at 78 C. and is then allowed to warm to room temperature and stir for 3 additional hours at room temperature. After that time the reaction mixture is poured in 125 mL of HCl 2N and extracted with tert-butyl-methyl ether (TBME, 2100 mL). The combined organic layers are washed with 100 mL water and 100 mL brine, then dried over sodium sulphate, filtered and the sok vent is evaporated on rotary evaporator to obtain compound 105 (beige powder, 4.25 g, 96% yield).

(12) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =8.05 (1H, s), 8.00 (1H, s), 4.03 (3H, s), 3.12 (2H, t, J=8.0 Hz), 1.74-1.67 (2H, m), 1.40 (12H, s), 1.38 (12H, s), 1.45-1.20 (6H, m), 0.90 (3H, t, J=7.0 Hz);

(13) ##STR00123##

(14) e) The synthesis of 1,4-bis(5-bromo-2-furyl)-2,5-bis(2-butyloctyl)pyrrolo[3,4-c]pyrrole-3,6-dione 106 is, for example, described in patent application WO2011/144566.

(15) In a 200 mL flask equipped with a condenser, a mechanical stirrer, an argon inlet and a thermometer is introduced compound 105 (600 mg, 1.03 mmol) and 1,4-bis(5-bromo-2-furyl)-2,5-bis(2-butyloctyl)pyrrolo[3,4-c]pyrrole-3,6-dione 106 (746 mg, 0.98 mmol). The flask is flushed with argon and dry THF (50 mL) is added by syringe. The resulting red solution is heated to reflux and a previously prepared solution of palladium(II) acetate (6.59 mg, 0.029 mmol) and 2-(di-tert-butylphosphino)-1-phenylpyrrole (33.7 mg, 0.117 mmol) in 5 mL THF is added at 50 C. The resulting mixture is stirred for 5 minutes at reflux temperature. After that time finely crushed lithium hydroxide monohydrate (258 mg, 6.16 mmol) is added in a single portion at 60 C. and is stirred at reflux temperature for 2 hours. After that time, the heating is stopped and water (75 mL) is added. The polymer is filtered, and washed with water.

(16) The filtered solid is then put in a flask containing 70 mL chloroform and 75 mL of a 3% sodium cyanide aqueous solution and is heated under vigorous stirring at 55 C. overnight. The phases are separated, and the organic phase is washed with water (380 mL), and two thirds of the chloroform is then evaporated. Ethanol (150 mL) is added to precipitate the product, which is filtered on a Bchner funnel. The dried solid is then purified by soxhlet extraction, first with cyclohexane (160 mL, 19 h). The fraction soluble in cyclohexane is discarded and the remaining solid is then subjected to soxhlet extraction with tetrahydrofuran (160 mL, 3 h). The solution is concentrated, the product is precipitated in ethanol, filtered and dried under reduced pressure to afford the polymer P-1 (700 mg, yield 77%).

(17) High temperature GPC: M.sub.w=41500, PD 2.20.

Example 2

Synthesis of Polymer P-2

(18) ##STR00124##

(19) The synthesis of 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-hexyldecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione 107 is, for example, described in WO2008/000664 and Y. Geerts; Tetrahedron 66 (2010) 1837-1845. In a 200 mL flask equipped with a condenser, a mechanical stirrer, an argon inlet and a thermometer is introduced compound 105 (614 mg, 1.05 mmol) and 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-hexyldecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione 107 (907 mg, 1.00 mmol). The flask is flushed with argon and dry THF (50 mL) is added by syringe. The resulting red solution is heated to reflux and a previously prepared solution of palladium(II) acetate (6.7 mg, 0.030 mmol) and 2-(di-tert-butylphosphino)-1-phenylpyrrole (34.5 mg, 0.120 mmol) in 5 mL THF is added at 50 C. The resulting mixture is stirred for 5 minutes at reflux temperature. After that time finely crushed lithium hydroxide monohydrate (264 mg, 6.30 mmol) is added in a single portion at 60 C. and is stirred at reflux temperature for 2 hours. After that time, the heating is stopped and water (75 mL) is added. The polymer is filtered, and washed with water.

(20) The filtered solid is then put in a flask containing 70 mL chloroform and 75 mL of a 3% sodium cyanide aqueous solution and is heated under vigorous stirring at 55 C. overnight. The organic phase is washed with water (380 mL), and two thirds of the chloroform is then evaporated. Ethanol (150 mL) is added to precipitate the product, which is filtered on a Bchner funnel. The dried solid is then purified by soxhlet extraction, first with cyclohexane (160 mL, 2 h), and then with tetrahydrofuran (160 mL, 4 h). The fractions soluble in cyclohexane and tetrahydrofuran are discarded and the remaining solid is then subjected to soxhlet extraction with chloroform (160 mL, 3 h). The solution is concentrated, the product is precipitated in ethanol, filtered and dried under reduced pressure to afford the polymer P-2 (1000 mg, yield 92%).

(21) High temperature GPC: M.sub.w=49200, PD 2.12.

Example 3

Synthesis of Polymer P-3

(22) ##STR00125##

(23) a) In a flask, equipped with a condenser, is introduced under argon compound 104 (4.99 g, 15.0 mmol), ethanol (40 mL) and 9N KOH in water (8.33 mL, 75.0 mmol). The resulting mixture is stirred 1 h at room temperature and 2 h at reflux. As the conversion is incomplete 8.33 mL of 9N KOH in water and 50 mL ethanol are added again, and the resulting solution is heated at reflux for 5 h. After that time the solvent is removed on rotary evaporator, tert-butyl-methyl ether (100 mL) is added followed by 100 mL of a 2N HCl (aq.) solution. Phases are separated and the aqueous phase is extracted with 75 mL of tert-butyl-methyl ether. The combined organic phases are then washed with water (100 mL) and brine (100 mL), then dried over sodium sulphate, filtered and the solvent is evaporated on rotary evaporator. The crude is then recrystallized from chloroform (22 mL), and the obtained crystals are then washed with cold chloroform and dried under vacuum to obtain the pure product 108 (beige crystals, 4.098 g, yield: 85%).

(24) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =7.86 (1H, d, J=5.5 Hz), 7.60 (1H, d, J=5.5 Hz), 7.48 (2H, d, J=5.2 Hz), 3.32 (2H, t, J=8.0 Hz), 1.85-1.77 (2H, m), 1.55-1.48 (2H, m), 1.42-1.33 (4H, m), 0.90 (3H, t, J=7.0 Hz); .sup.13C (100.1 MHz, CDCl.sub.3), =174.5, 136.9, 136.8, 136.6, 135.4, 132.3, 125.1, 124.9, 124.8, 124.0, 122.0, 32.1, 31.7, 31.6, 29.7, 22.6, 14.1.

(25) ##STR00126##

(26) b) In a 3-neck flask equipped with a condenser are introduced, under nitrogen, compound 108 (1.75 g, 5.50 mmol), N,N-dicyclohexylcarbodiimide (DCC, 1.25 g, 6.05 mmol), 4-pyrrolidinopyridine (81 mg, 0.55 mmol) and dichloromethane (20 mL). To this mixture is added at room temperature phenol (569 mg, 6.05 mmol). After one hour at room temperature, the mixture is stirred at reflux for 1 h. The white suspension is then filtered over Hyflo, and washed with dichloromethane. The filtrate is concentrated on rotary evaporator to get 2.97 g of crude beige crystals. The crude is then purified by flash chromatography (gradient, Toluene/cyclohexane from 0:100 to 25:75) to obtain the pure product 109 (white crystals, 1.88 g, yield: 87%).

(27) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =7.76 (1H, d, J=5.5 Hz), 7.59 (1H, d, J=5.5 Hz), 7.53-7.47 (4H, m), 7.36-7.32 (3H, m), 3.30 (2H, t, J=8.0 Hz), 1.86-1.79 (2H, m), 1.53-1.48 (2H, m), 1.36-1.31 (4H, m), 0.89 (3H, t, J=7.0 Hz); .sup.13C (100.1 MHz, CDCl.sub.3), =167.3, 150.8, 136.8, 136.1, 135.6, 135.1, 132.2, 129.6 (2C), 126.0, 125.0, 124.8, 124.4, 123.8, 122.7, 121.5 (2C), 32.1, 31.7, 31.6, 29.7, 22.5, 14.0.

(28) ##STR00127##

(29) c) In a 3-neck flask equipped with a condenser and an addition funnel are introduced, under nitrogen, compound 109 (1.776 g, 4.50 mmol) and tetrahydrofuran (THF, 13 mL) followed by isopropoxypinacolborane (1.515 g, 8.14 mmol). The resulting solution is then cooled to 78 C. and a previously prepared lithium diisopropylamide solution (LDA, 1.73 mmol in 7 mL THF) is added dropwise. The reaction mixture is left to stir 1 h at 78 C. and is then allowed to warm to room temperature and stir for 1 additional hour at room temperature. After that time the reaction mixture is poured in 50 mL of HCl 2N and extracted with tert-butyl-methyl ether (TBME, 250 mL). The combined organic layers are washed with 50 mL water and 50 mL brine, then dried over sodium sulphate, filtered and the solvent is evaporated on rotary evaporator. The crude is then recrystallized from diisopropylether, and the obtained crystals are then washed with diisopropylether and dried under vacuum to obtain the pure product 110 (white crystals, 1.325 g, yield: 45%).

(30) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =8.20 (1H, s), 8.10 (1H, s), 7.52-7.48 (2H, m), 7.37-7.30 (3H, m), 3.30 (2H, t, J=8.0 Hz), 1.83-1.77 (2H, m), 1.53-1.45 (2H, m), 1.42 (12H, s), 1.38 (12H, s), 1.34-1.27 (4H, m), 0.86 (3H, t, J=7.2 Hz).

(31) ##STR00128##

(32) The synthesis of 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-hexyldecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione is, for example, described in WO2008/000664 and Y. Geerts; Tetrahedron 66 (2010) 1837-1845. In a 200 mL flask equipped with a condenser, a mechanical stirrer, an argon inlet and a thermometer is introduced the bis-boronic ester 110 (557 mg, 0.861 mmol) and 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-hexyldecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione 111 (744 mg, 0.82 mmol). The flask is flushed with argon and dry THF (50 mL) is added by syringe. The resulting red solution is heated to reflux and a previously prepared solution of palladium(II) acetate (5.52 mg, 0.025 mmol) and 2-(di-tert-butylphosphino)-1-phenylpyrrole (28.3 mg, 0.098 mmol) in 5 mL THF is added at 50 C. The resulting mixture is stirred for 5 minutes at reflux temperature. After that time finely crushed lithium hydroxide monohydrate (218 mg, 5.17 mmol) is added in a single portion at 60 C. and is stirred at reflux temperature for 3 hours. After that time, the heating is stopped and water (75 mL) is added. The polymer is filtered, and washed with water.

(33) The filtered solid is then put in a flask containing 70 mL chloroform and 75 mL of a 3% sodium cyanide aqueous solution and is heated under vigorous stirring at 55 C. overnight. The phases are separated and the organic phase is washed with water (380 mL), and two thirds of the chloroform is then evaporated. Ethanol (150 mL) is added to precipitate the product, which is filtered on a Bchner funnel. The dried solid is then purified by soxhlet extraction, first with cyclohexane (160 mL, 18 h) and with tetrahydrofuran (160 mL, 8 h). The fractions soluble in cyclohexane and tetrahydrofuran are discarded and the remaining solid is then subjected to soxhlet extraction with chloroform (160 mL, 3 h). The solution is concentrated, the product is precipitated in ethanol, filtered and dried under reduced pressure to afford the polymer P-3 (780 mg, yield 84%).

(34) High temperature GPC: M.sub.w=82800, PD 1.98.

Example 4

Synthesis of Polymer P-4

(35) ##STR00129##

(36) a) In a flask equipped with a condenser and an addition funnel are introduced compound 104 (1.33 g, 4.00 mmol) and 1-dodecanol (11.18 g, 60 mmol). The flask is flushed with argon and dibutyloxostannane (99.5 mg, 0.40 mmol) are added under argon at room temperature. The resulting solution is then heated to 190 C. under reduced pressure (200 mbar). After one hour an additional amount of 200 mg of dibutyloxostannane were added and the mixture stirred overnight at 190 C. under reduced pressure. After that time cyclohexane (15 mL) is added and the reaction mixture is directly purified by flash chromatography (eluent: toluene/cyclohexane 2:3) to get the pure product 112 (yellow oil, 1.606 g, yield: 82%).

(37) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =7.54 (1H, d, J=5.5 Hz), 7.53 (1H, d, J=5.5 Hz), 7.45 (1H, d, J=5.5 Hz), 7.42 (1H, d, J=5.5 Hz), 4.45 (2H, t, J=7.0 Hz), 3.13 (2H, d, J=8.0 Hz), 1.82 (2H, quint., J=7.0 Hz), 1.76-1.70 (2H, m), 1.50-1.42 (4H, m), 1.38-1.23 (20H, m), 0.92 (6H, m); .sup.13C (100.1 MHz, CDCl.sub.3), =169.2, 136.7, 135.3, 135.0, 134.2, 131.9, 124.5, 124.5, 124.3, 124.2, 123.7, 65.5, 31.9, 31.8, 31.7 (2C), 29.8, 29.6 (4C), 29.5, 29.3, 29.2, 28.7, 26.1, 22.6, 14.1 (2C).

(38) ##STR00130##

(39) b) In a 3-neck flask equipped with a condenser and an addition funnel are introduced, under nitrogen, compound 112 (1.801 g, 3.70 mmol) and tetrahydrofuran (THF, 13 mL) followed by isopropoxypinacolborane (1.515 g, 8.14 mmol). The resulting solution is then cooled to 78 C. and a previously prepared lithium diisopropylamide solution (LDA, 7.58 mmol in 7 mL THF) is added dropwise. The reaction mixture is left to stir 1 h at 78 C. and is then allowed to warm to room temperature and stir for 3 additional hours at room temperature. After that time the reaction mixture is poured in 50 mL of HCl 2N and extracted with tert-butyl-methyl ether (TBME, 250 mL). The combined organic layers are washed with 50 mL water and 50 mL brine, then dried over sodium sulphate, filtered and the solvent is evaporated on rotary evaporator. The crude is then triturated in warm isopropanol, filtered, and the obtained crystals are then washed with isopropanol and dried under vacuum to obtain the pure product 113 (white crystals, 1.836 g, yield: 67%).

(40) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =8.05 (1H, s), 8.01 (1H, s), 4.44 (2H, t, J=6.8 Hz), 3.12 (2H, d, J=8.0 Hz), 1.81 (2H, quint., J=6.8 Hz), 1.74-1.69 (2H, m), 1.48-1.21 (24H, m), 1.40 (12H, s), 1.37 (12H, s), 0.91-0.85 (6H, m).

(41) ##STR00131##

(42) The synthesis of 1,4-bis(5-bromo-2-furyl)-2,5-bis(2-butyloctyl)pyrrolo[3,4-c]pyrrole-3,6-dione 106 is, for example, described in WO2011/144566.

(43) c) In a 200 mL flask equipped with a condenser, a mechanical stirrer, an argon inlet and a thermometer is introduced the bis-boronic ester 113 (550 mg, 0.74 mmol) and 1,4-bis(5-bromo-2-furyl)-2,5-bis(2-butyloctyl)pyrrolo[3,4-c]pyrrole-3,6-dione 106 (541 mg, 0.71 mmol). The flask is flushed with argon and dry tetrahydrofuran (THF, 50 mL) is added by syringe. The resulting solution is heated to reflux and a previously prepared solution of palladium(II) acetate (4.78 mg, 0.021 mmol) and 2-(di-tert-butylphosphino)-1-phenylpyrrole (24.5 mg, 0.085 mmol) in 5 mL THF is added at 50 C. The resulting mixture is stirred for 5 minutes at reflux temperature. After that time finely crushed lithium hydroxide monohydrate (187 mg, 4.47 mmol) is added in a single portion at 55 C. and is stirred at reflux temperature for 2 hours. After that time, the heating is stopped and water (75 mL) is added. The polymer is filtered, and washed with water. The filtered solid is then put in a flask containing 70 mL chloroform and 75 mL of a 3% sodium cyanide aqueous solution and is heated under vigorous stirring at 55 C. overnight. The phases are separated and the organic phase is washed with water (380 mL), and two thirds of the chloroform is then evaporated. Ethanol (100 mL) is added to precipitate the product, which is filtered on a Bchner funnel. The dried solid is then purified by soxhlet extraction, first with cyclohexane (160 mL, 20 h). The fraction soluble in cyclohexane is discarded and the remaining solid is then subjected to soxhlet extraction with tetrahydrofuran (160 mL, 5 h). The solution is concentrated, the product is precipitated in ethanol, filtered and dried under reduced pressure to afford the polymer P-4 (524 mg, yield 70%).

(44) High temperature GPC: M.sub.w=61700, PD 1.88.

Example 5

Synthesis of Polymer P-5

(45) ##STR00132##

(46) The synthesis of 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-hexyldecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione is, for example, described in WO2008/000664 and Y. Geerts; Tetrahedron 66 (2010) 1837-1845. In a 200 mL flask equipped with a condenser, a mechanical stirrer, an argon inlet and a thermometer is introduced the bis-boronic ester 113 (665 mg, 0.90 mmol) and 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-hexyldecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione 107 (777 mg, 0.86 mmol). The flask is flushed with argon and dry tetrahydrofuran (THF, 55 mL) is added by syringe. The resulting red solution is heated to reflux and a previously prepared solution of palladium(II) acetate (5.77 mg, 0.026 mmol) and 2-(di-tert-butylphosphino)-1-phenylpyrrole (29.6 mg, 0.103 mmol) in 5 mL THF is added at 50 C. The resulting mixture is stirred for 5 minutes at reflux temperature. After that time finely crushed lithium hydroxide monohydrate (227 mg, 5.40 mmol) is added in a single portion at 55 C. and is stirred at reflux temperature for 2 hours. After that time, the heating is stopped and water (75 mL) is added. The polymer is filtered, and washed with water. The filtered solid is then put in a flask containing 50 mL chloroform and 75 mL of a 2.5% sodium cyanide aqueous solution and is heated under vigorous stirring at 55 C. for 3 h. The organic phase is separated, and the organic fraction is treated again with 75 mL of a 2.5% sodium cyanide aqueous solution at 55 C. for 2.5 h. The organic phase is then separated and washed 3 times with water. Two thirds of the chloroform is then evaporated. Ethanol (150 mL) is added to precipitate the product, which is filtered on a Bchner funnel and washed with ethanol. The dried solid is then purified by soxhlet extraction, first with acetone (160 mL, 1 h), cyclohexane (160 mL, 16 h) and with tetrahydrofuran (160 mL, 3 h). The fractions soluble in acetone, cyclohexane and tetrahydrofuran are discarded and the remaining solid is then subjected to soxhlet extraction with chloroform (160 mL, 2.5 h). The solution is concentrated, the product is precipitated in ethanol, filtered and dried under reduced pressure to afford the polymer P-5 (870 mg, yield 83%).

(47) High temperature GPC: M.sub.w=41000, PD 1.80.

Example 6

Synthesis of Polymer P-6

(48) ##STR00133##

(49) a) In a 500 mL flask equipped with a condenser is introduced, under nitrogen, methyl 5-hexylthieno[3,2-g]benzothiophene-4-carboxylate 104 (2.95 g, 8.88 mmol) and toluene (200 mL). Diisobutylaluminum hydride (DIBAL-H, 1.0 M in heptane, 17.2 mL, 17.2 mmol) is then slowly added at 78 C., and the resulting mixture is stirred 2 h at 78 C. The reaction mixture is then poured into 1M HCl (200 mL), and extracted with tert-butyl-methyl-ether (TBME, 100 mL) and dichloromethane (2200 mL). The combined organic fractions are dried over sodium sulphate, filtered and the solvent was evaporated on rotary evaporator to obtain 2.45 g of a yellow oil which crystallized upon cooling. The crude is then purified by column chromatography (Silica gel, Hexane/EtOAc/dichloromethane 6:2:1) to obtain the product 114 (yellow solid, 2.05 g, yield: 77%).

(50) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =7.65 (1H, d, J=5.5 Hz), 7.51 (1H, d, J=5.5 Hz), 7.45 (1H, d, J=5.5 Hz), 7.42 (1H, d, J=5.5 Hz), 5.12 (2H, s), 3.14 (2H, t, J=8.0 Hz), 1.72-1.64 (2H, m), 1.52-1.45 (2H, m), 1.37-1.31 (4H, m), 0.91 (3H, t, J=7.0 Hz); .sup.13C (100.1 MHz, CDCl.sub.3), =137.4, 137.3, 133.7, 133.5, 132.0, 128.6, 124.4, 124.0, 123.7, 123.3, 60.2, 32.3, 31.7, 30.4, 29.7, 22.7, 14.1.

(51) ##STR00134##

(52) b) In a 500 mL flask equipped with a condenser is introduced compound 114 (2.05 g, 6.73 mmol) and dichloromethane (250 mL). MnO.sub.2 (5.85 g, 67.3 mmol) is then slowly added at room temperature, and the resulting mixture is stirred 5 days at room temperature. Upon completion of the reaction, the product is filtered over a pad of silica to remove manganese salts. The filtrate is concentrated on rotary evaporator and the crude dark brown oil is purified by column chromatography (Silica gel, Hexanes/EtOAC 10:1, r.f. 0.6). This affords compound 115 as a yellow oil which slowly crystallizes (1.65 g, yield: 81%).

(53) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =10.81 (1H, s), 8.48 (1H, d, J=5.5 Hz), 7.61 (1H, d, J=5.5 Hz), 7.55 (1H, d, J=5.3 Hz), 7.48 (1H, d, J=4.3 Hz), 3.45 (2H, t, J=8.0 Hz), 1.81-1.73 (2H, m), 1.53-1.44 (2H, m), 1.36-1.29 (4H, m), 0.90 (3H, t, J=7.0 Hz); .sup.13C (100.1 MHz, CDCl.sub.3), =191.4, 141.9, 139.2, 136.9, 135.1, 133.3, 126.6, 125.0, 124.9, 124.8, 123.6, 33.2, 31.6, 29.5, 29.2, 22.6, 14.1; GC/MS: (CI pos.): 303.18 (MH.sup.+).

(54) ##STR00135##

(55) c) In a 500 mL flask equipped with a condenser is introduced under nitrogen compound 115 (1.65 g, 5.45 mmol) and hydroxylamine hydrochloride (569 mg, 8.18 mmol), pyridine (100 mL) and ethanol (100 mL). The yellow solution is then heated at 80 C. overnight. After that time, the mixture is cooled to room temperature, solvents are evaporated on rotary evaporator, chloroform (300 mL) is added, and the organic phase is washed with water (2200 mL). The organic layer is then dried over sodium sulphate, and the solvent was evaporated on rotary evaporator. The crude is then purified by column chromatography (eluent: Hexane/EtoAc/CH.sub.2Cl.sub.2 10:1:1, rf=0.5) to afford product 116 as a 20:1 mixture of isomers (white solid, 1.45 g, yield: 84%).

(56) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =8.80 (1H, s), 8.09 (1H, d, J=5.5 Hz), 7.52 (1H, d, J=5.5 Hz), 7.43 (1H, d, J=5.5 Hz), 7.42 (1H, d, J=5.5 Hz), 3.13 (2H, t, J=8.0 Hz), 1.71-1.64 (2H, m), 1.50-1.42 (2H, m), 1.37-1.28 (4H, m), 0.90 (3H, m); .sup.13C (100.1 MHz, CDCl.sub.3), =149.5, 137.0, 135.4, 135.0, 132.6, 125.8, 124.6, 124.3, 123.6, 123.4, 120.9, 31.8, 31.7, 30.6, 29.5, 22.6, 14.1.

(57) ##STR00136##

(58) d) In a 500 mL round bottom flask equipped with a condenser is introduced, under nitrogen, compound 116 (1.30 g, 4.09 mmol), KOAc (100 mg) and acetic anhydride (100 mL). The yellow mixture is then heated at 150 C. for 4 h. After that time, the mixture is cooled to room temperature, and water (100 mL) is added followed by 5% NaOH solution. The product is then extracted with Et.sub.2O (3200 mL). The combined organic layers are dried over sodium sulphate, and the solvent is evaporated on rotary evaporator to obtain a brown oil. The crude is then purified by column chromatography (Silica, hexanes/ethyl acetate 90:10, Rf=0.75). This affords product 117 (colorless to yellow oil, 1.15 g, yield: 94%).

(59) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =7.63 (1H, d, J=5.5 Hz), 7.56 (1H, d, J=5.5 Hz), 7.54 (1H, d, J=5.5 Hz), 7.51 (1H, d, J=5.5 Hz), 3.27 (2H, t, J=7.8 Hz), 1.81-1.73 (2H, m), 1.51-1.43 (2H, m), 1.37-1.25 (4H, m), 0.90 (3H, m); .sup.13C (100.1 MHz, CDCl.sub.3), =141.3, 137.7, 137.1, 136.1, 132.0, 126.6, 125.7, 123.5, 123.4, 117.7, 103.3, 33.2, 31.6, 31.3, 29.3, 22.6, 14.1; GC/MS: (CI pos.): 300.19 (MH.sup.+).

(60) ##STR00137##

(61) e) In a 100 mL flask equipped with a condenser is introduced, under nitrogen, compound 117 (1.1 g, 3.67 mmol as a solution in 20 mL tetrahydrofuran). Under nitrogen, more tetrahydrofuran (THF, 80 mL) is then added. The yellow solution is cooled to 78 C. and n-butyllithium solution (2.7 M in heptane, 3.4 mL, 9.19 mmol) is added dropwise. The resulting yellow mixture is stirred for 1 h 20 at 78 C. After that time isopropoxy pinacol borane (2.05 g, 11.0 mmol) is added at 78 C. The mixture turns to a clear yellow solution. After 20 minutes at 78 C., the reaction mixture is allowed to warm to room temperature and is stirred 2 hours at room temperature. Then, water is added at 0 C. and the product is extracted with tert-butyl-methyl-ether (TBME, 100 mL) and dichloromethane (2100 mL). The combined organic fractions are dried over Na.sub.2SO.sub.4, filtered, concentrated on rotary evaporator. The crude yellow oil is recrystallized in acetonitrile and the powder is filtered and washed with cold acetonitrile to obtain product 118 (white powder, 1.81 g, yield: 89%).

(62) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =8.16 (1H, s); 8.05 (1H, s), 3.28 (2H, t, J=7.8 Hz), 1.77 (2H, q, J=7.8 Hz), 1.55-1.25 (6H, m), 1.41 (12H, s), 1.39 (12H, s), 0.89 (3H, t, J=6.8 Hz).

(63) ##STR00138##

(64) f) The synthesis of 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-hexyldecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione 107 is, for example, described in WO2008/000664 and Y. Geerts; Tetrahedron 66 (2010) 1837-1845. In a 250 mL flask equipped with a condenser, a mechanical stirrer, a nitrogen bubbler and a thermometer is introduced bis-boronic ester 118 (469 mg, 0.85 mmol) and 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-hexyldecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione 107 (739 mg, 0.81 mmol). The flask is flushed with nitrogen and dry THF (40 mL) is added by syringe. The resulting red solution is heated to 60 C. and a solution of palladium(II) acetate (5.5 mg, 0.024 mmol) and 2-(di-tert-butylphosphino)-1-phenylpyrrole (27.9 mg, 0.097 mmol) in 10 mL THF is added. The resulting mixture is stirred for 5 minutes at reflux temperature. After that time finely crushed lithium hydroxide monohydrate (214 mg, 5.10 mmol) is added in a single portion at 60 C. and is stirred at reflux temperature for 4 hours. The reaction mixture is poured into ethanol (300 mL) and the precipitate is filtered on a Bchner funnel. The solid is then washed with 200 mL ethanol and 200 mL deionised water. The filtered solid is then put in a flask containing 200 mL chloroform and 200 mL of a 2% sodium cyanide aqueous solution and is heated under vigorous stirring at 60 C. overnight. The phases are separated, and the organic phase is washed with 100 mL water, and two thirds of the chloroform is then evaporated. Ethanol is added to precipitate the product, which is filtered on a Bchner funnel, washed with 300 mL ethanol and dried in the oven. The treatment with sodium cyanide is then repeated a second time. The dried solid is then purified by soxhlet extraction, first with tetrahydrofuran (200 mL, 5 h). The fraction soluble in tetrahydrofuran is discarded and the remaining solid is then subjected to soxhlet extraction with chloroform (200 mL, 4 h). The green solution is concentrated, the product is precipitated in ethanol, filtered and dried under reduced pressure to afford the polymer P-6 (696 mg, yield 82%).

(65) High temperature GPC: M.sub.w=45600, M.sub.n=19400, PD 2.34.

Example 7

Synthesis of Polymer P-7

(66) ##STR00139##

(67) The synthesis of 1,4-bis(5-bromo-2-furyl)-2,5-bis(2-butyloctyl)pyrrolo[3,4-c]pyrrole-3,6-dione 106 is, for example, described in WO2011/144566.

(68) In a 20 mL flask equipped with a condenser, a mechanical stirrer, an argon inlet and a thermometer is introduced the bis-boronic ester 118 (492 mg, 0.89 mmol) and 1,4-bis(5-bromo-2-furyl)-2,5-bis(2-butyloctyl)pyrrolo[3,4-c]pyrrole-3,6-dione 106 (648 mg, 0.85 mmol). The flask is flushed with argon and dry THF (45 mL) is added by syringe. The resulting solution is heated to reflux and a previously prepared solution of palladium(II) acetate (5.72 mg, 0.026 mmol) and 2-(di-tert-butylphosphino)-1-phenylpyrrole (29.3 mg, 0.102 mmol) in 5 mL THF is added at 50 C. The resulting mixture is stirred for 5 minutes at reflux temperature. After that time finely crushed lithium hydroxide monohydrate (225 mg, 5.36 mmol) is added in a single portion at 60 C. and is stirred at reflux temperature for 2 hours. After that time, the heating is stopped and water (75 mL) is added. The polymer is filtered, and washed with water. The filtered solid is then put in a flask containing 70 mL chloroform and 75 mL of a 3% sodium cyanide aqueous solution and is heated under vigorous stirring at 55 C. overnight. The phases are separated, and the organic phase is washed with water (380 mL), and two thirds of the chloroform is then evaporated. Ethanol (150 mL) is added to precipitate the product, which is filtered on a Bchner funnel. The dried solid is then purified by soxhlet extraction, first with cyclohexane (160 mL, 21 h). The fraction soluble in cyclohexane is discarded and the remaining solid is then subjected to soxhlet extraction with tetrahydrofuran (160 mL, 24 h). The solution is concentrated, the product is precipitated in ethanol, filtered and dried under reduced pressure to afford a first fraction of polymer P-6 (410 mg, yield 53%, M.sub.w=66400, PD=2.01). The remaining solid is then subjected to another soxhlet extraction with chloroform (160 mL, 2.5 h). The solution is concentrated, the product is precipitated in ethanol, filtered and dried under reduced pressure to afford the higher molecular weight fraction of polymer P-7 (258 mg, yield 34%, M.sub.w=81600, PD=2.39).

(69) High temperature GPC: Chloroform fraction: M.sub.w=81600, PD 2.39.

Example 8

Synthesis of Polymer P-8

(70) ##STR00140##

(71) a) Compound 120 can be for example prepared from ((6,6-dibromo-N,N-(2-hexyldecanyl)isoindigo) using similar method to the one described in Klapars, A.; Buchwald, S. L.; J. Am. Chem. Soc., 2002, 124, 14844-14845.

(72) In a 200 mL flask equipped with a condenser, a mechanical stirrer, a nitrogen bubbler and a thermometer is introduced bis-boronic ester 118 (434 mg, 0.79 mmol) and compound 120 (722 mg, 0.75 mmol), and dry THF (40 mL) is added by syringe. The resulting red solution is heated to 60 C. and a solution of palladium(II) acetate (5.1 mg, 0.022 mmol) and 2-(di-tert-butylphosphino)-1-phenylpyrrole (25.9 mg, 0.090 mmol) in 10 mL THF is added. The resulting mixture is stirred for 5 minutes at reflux temperature. After that time finely crushed lithium hydroxide monohydrate (198 mg, 4.72 mmol) is added in a single portion at 60 C. and is stirred at reflux temperature for 6 hours. The reaction mixture is poured into ethanol (400 mL) and the precipitate is filtered on a Bchner funnel. The solid is then washed with 200 mL ethanol and 200 mL deionised water. The filtered solid is then put in a flask containing 150 mL chloroform and 150 mL of a 3% sodium cyanide aqueous solution and is heated under vigorous stirring at 60 C. overnight. The phases are then separated, and the organic phase is washed with water (3100 mL), and the chloroform is then evaporated. Ethanol is added to precipitate the product, which is filtered on a Bchner funnel, washed with water (200 mL) and ethanol (50 mL) and dried in the oven. The treatment with sodium cyanide is then repeated a second time. The dried solid is then purified by soxhlet extraction, first with acetone (200 mL, 5 h). The fraction soluble in acetone is discarded and the remaining solid is then subjected to soxhlet extraction with cyclohexane (200 mL, 7 h). The solvent is then evaporated, and the product is precipitated in ethanol, filtered and dried under reduced pressure to afford the polymer P-8 (640 mg, yield 85%).

(73) High temperature GPC: M.sub.w=19500, PD=1.38.

Example 9

Synthesis of Monomer 125

(74) ##STR00141##

(75) a) To a solution of 1-octyne in tetrahydrofuran (THF, 180 mL) previously cooled to 78 C. is added under nitrogen n-buyllithium (2.5 M solution in hexane, 33.2 mL, 83 mmol). The colorless mixture is stirred 1 h and is then treated with N-methoxy-methylacetamide in THF (20 mL). The reaction mixture is stirred at room temperature for 4 h. After that time 3M HCl solution (100 mL) is added. Tert-butyl-methyl ether (TBME) is added and the reaction mixture is extracted with TBME (3100 mL). The combined organic layers are washed with saturated NaHCO.sub.3, dried over magnesium sulphate and the volatiles are removed on rotary evaporator. The residue is then purified by flash column chromatography (eluent: ethyl acetate/hexane 1:10) to obtain product 121 (colorless oil, 6.2 g, yield: 64%).

(76) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =2.35 (2H, t, J=7.2 Hz), 2.31 (3H, s), 1.57 (2H, quint., J=7.2 Hz), 1.43-1.35 (2H, m), 1.33-1.25 (4H, m), 0.89 (3H, t, J=7.0 Hz); .sup.13C (100.1 MHz, CDCl.sub.3), =184.9, 94.2, 81.4, 32.7, 31.2, 28.5, 27.6, 22.4, 18.9, 14.0.

(77) ##STR00142##

(78) b) In a 500 mL flask equipped with a condenser is introduced compound 102 (8.87 g, 15.76 mmol) and dimethyl formamide (DMF, 150 mL) under nitrogen. After, compound 121 (4.8 g, 31.53 mmol) is added under nitrogen at room temperature, followed by and Pd(OAc).sub.2 (354 mg, 1.58 mmol) and tributylamine (5.84 g, 31.53 mmol). The reaction mixture is then heated to 130 C. for 4 h. After that time the solution is cooled to room temperature and poured into water (200 mL). Dichloromethane is added and the aqueous phase is extracted with dichloromethane (2200 mL). The combined organic phases are dried over magnesium sulphate, filtered and the solvent was evaporated on rotary evaporator to give a dark brown oil. The crude dark brown oil is purified by two successive flash column chromatographies: first with hexanes/ethyl acetate 20:1 as eluent, and then with cyclohexane/toluene 1:1 as eluent to obtain product 122 (oil, 3.45 g, 47% yield).

(79) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =7.58 (1H, s), 7.33 (1H, s), 2.97 (2H, t, J=8.0 Hz), 2.68 (3H, s), 1.75-1.66 (2H, m), 1.47-1.41 (2H, m), 1.37-1.31 (4H, m), 0.90 (3H, t, J=7.0 Hz); .sup.13C (100.1 MHz, CDCl.sub.3), =206.7, 141.5, 141.0, 138.1, 137.9, 135.9, 134.5, 133.3, 130.1, 130.0, 129.2, 33.1, 31.8, 31.5, 29.7, 29.6, 22.6, 14.0, 0.2 (6C); GC/MS: (CI pos.): 461.36 (MH.sup.+).

(80) ##STR00143##

(81) c) In a 500 mL flask, equipped with a condenser, is introduced under nitrogen atmosphere compound 122 (3.40 g, 7.38 mmol) and THF (100 mL). Tetrabutyl ammonium fluoride (TBAF, 5.12 g, 16.23 mmol) is then slowly added at room temperature as a THF solution, and the resulting solution is stirred 2 h at room temperature. After that time the solution is poured into water (300 mL), and extracted with tert-butyl-methyl-ether (1200 mL) and dichloromethane (2200 mL). The combined organic fractions are dried over sodium sulphate, filtered and the solvent is evaporated on rotatory evaporator. The crude dark brown oil is purified by column chromatography (Silica gel, cyclohexane/toluene, 60:40 then 40:60, Rf=0.45 in cyclohexane/toluene 60:40. This affords the desired product 123 (dark yellow oil, 2.1 g, yield: 90%).

(82) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =7.52 (1H, d, J=5.5 Hz), 7.47 (1H, d, J=5.3 Hz), 7.44 (1H, d, J=5.5 Hz), 7.27 (1H, d, J=5.3 Hz), 2.96 (2H, m), 2.67 (3H, s), 1.74-1.66 (2H, m), 1.47-1.40 (2H, m), 1.36-1.29 (4H, m), 0.90 (3H, m); .sup.13C (100.6 MHz, CDCl.sub.3), =206.1, 136.6, 134.4, 133.6, 133.1, 132.1, 130.4, 125.1, 124.7, 123.5, 122.8, 32.9, 31.9, 31.6 (2C), 29.7, 22.6, 14.0; GC/MS: (CI pos.): 317.14 (MH.sup.+).

(83) ##STR00144##

(84) d) In a 500 mL flask, equipped with a Dean-Stark apparatus, is introduced compound 123 (1.9 g, 6.00 mmol), p-toluenesulfonic acid (230 mg, 1.20 mmol), ethyleneglycol (0.82 g, 13.21 mmol) and toluene (200 mL). The resulting solution is heated at reflux for 3 days. After that time, approximately of the start. material has reacted. The reaction is stopped. The mixture is left to cool to room temp. Water is added (200 mL) followed by tert-butyl-methyl-ether (150 mL). The phases are separated and the organic phase is washed with a saturated NaHCO.sub.3 aqueous solution (100 mL). The combined organic fractions are dried over anhydrous sodium sulfate and filtered. The solvents are removed on rotatory evaporated to get the crude material (yellow oil). The crude is then further purified by column chromatography (Silica, eluent: cyclohexane/toluene 40:60) to afford the product as a yellow oil (1.12 g) and unreacted starting material (630 mg). The unreacted starting material is reacted again under similar conditions for 72 h. After purification, another fraction of product is collected (462 mg, yellow oil). Total amount of product 124 obtained after purification: 1.58 g (yellow oil, 73% yield).

(85) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =8.2 (1H, d, J=5.5 Hz), 7.50 (1H, d, J=5.5 Hz), 7.39 (1H, d, J=5.5 Hz), 7.34 (1H, d, J=5.5 Hz), 4.06 (2H, m), 3.73 (2H, m), 3.27 (2H, m), 1.88 (3H, s), 1.76-1.70 (2H, m), 1.60-1.55 (2H, m), 1.44-1.37 (4H, m), 0.95 (3H, m); .sup.13C (100.6 MHz, CDCl.sub.3), =138.3, 135.1, 133.5, 133.4, 132.6, 132.2, 127.1, 124.1, 123.7, 122.7, 111.0, 64.1 (2C), 32.4, 31.9, 31.7, 30.3, 27.8, 22.7, 14.1; GC/MS: (CI pos.): 361.15 (MH.sup.+).

(86) ##STR00145##

(87) e) In a 250 mL flask is introduced under a nitrogen atmosphere compound 124 (as a solution in 20 mL tetrahydrofuran) and tetrahydrofuran (80 mL). The yellow solution is then cooled to 78 C. and n-butyllithium (2.5 M solution, 2.68 mL, 6.71 mmol) is added dropwise under nitrogen. The resulting mixture is stirred for 1 h 20 at 78 C. After that time isopropoxy pinacol borane is added at 78 C. The mixture turns to a clear yellow solution. After 20 minutes at 78 C., the mixture is allowed to warm to room temperature and stirred 2 hours at room temperature. Then, water is added at 0 C., followed by 1 M HCl (15 mL). Phases are separated and the aqueous phase is extracted with tert-butyl-methyl ether (TBME, 100 mL) and dichloromethane (2100 mL). The combined organic fractions are then dried over Na.sub.2SO.sub.4, filtered, concentrated on rotavap. The crude yellow oil is then treated several times with active charcoal (500 mg) in hexanes and filtered to remove side products. Solvent is then evaporated to obtain compound 125 (yellow solid, 789 mg, yield: 42%)

(88) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =8.68 (1H, s), 8.00 (1H, s), 4.05 (2H, m), 3.73 (2H, m), 3.27 (2H, m), 1.87 (3H, s), 1.73-1.67 (2H, m), 1.58-1.52 (2H, m), 1.44-1.23 (4H, m), 1.39 (12H, s), 1.37 (12H, s) 0.93 (3H, m).

Example 10

Synthesis of Polymer P-9

(89) ##STR00146##

(90) a) In a 100 mL flask previously flushed with nitrogen and equipped with a condenser, is introduced under a nitrogen atmosphere compound 102 (2.00 g, 3.56 mmol) and N,N-dimethylformamide (DMF, 30 mL). Methyl 3-trimethylsilylprop-2-ynoate 126 (1.11 g, 7.11 mmol) is then added at room temperature, followed by Pd(OAc).sub.2 (79.8 mg, 0.356 mmol) and tributylamine (1.32 g, 7.11 mmol). The resulting solution is then heated at 135 C. for 5 h. After that time the solution is cooled to room temperature and poured into water (200 mL) and extracted with dichloromethane (2200 mL). The combined organic fractions are dried over sodium sulphate, filtered and the solvent is evaporated on rotary evaporator to obtain a dark brown oil. The crude is then further purified by column chromatography (Cyclohexane/toluene 2:1) to obtain product 127 (white solid, 0.50 g, yield: 30%).

(91) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =7.79 (1H, s), 7.53 (1H, s), 4.00 (3H, s), 0.46 (9H, s), 0.42 (9H, s), 0.40 (9H, s); .sup.13C (100.1 MHz, CDCl.sub.3), =171.0, 141.6, 141.1, 140.2, 138.8, 138.6, 135.3, 133.1, 131.8, 130.1, 129.8, 52.2, 1.4 (3C), 0.2 (3C), 0.3 (3C); GC/MS: (CI pos.): 465.16 (MH.sup.+).

(92) ##STR00147##

(93) b) In a 500 mL flask is introduced, under a nitrogen atmosphere compound 127 (350 mg, 0.75 mmol) and tetrahydrofurane (THF, 10 mL). A solution of tetrabutylammonium fluoride trihydrate (0.83 g, 2.64 mmol) in tetrahydrofurane (10 mL) is then slowly added at room temperature. The resulting solution is stirred 2 h at room temperature. After that time the solution is poured into water (100 mL), and extracted with tert-butyl-methyl ether (1100 mL) and dichloromethane (2100 mL). The combined organic fractions are dried over sodium sulphate, filtered and the solvent is evaporated on rotary evaporator. The crude is then purified by column chromatography (cyclohexane/toluene 1:1) to obtain compound 128 (white solid, 177 mg, yield: 95%).

(94) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =8.57 (1H, s), 8.32 (1H, d, J=5.5 Hz), 7.53 (1H, d, J=5.5 Hz), 7.49 (1H, d, J=5.5 Hz), 7.45 (1H, d, J=5.5 Hz), 4.02 (3H, s); .sup.13C (100.1 MHz, CDCl.sub.3), =167.3, 138.0, 136.1, 135.5, 134.8, 125.7, 125.6, 125.2, 125.1, 124.3, 121.9, 52.0; GC/MS: (CI pos.): 249.05 (MH.sup.+).

(95) ##STR00148##

(96) c) In a 3-neck flask equipped with a condenser and an addition funnel are introduced, under nitrogen, compound 128 (1.614 g, 6.5 mmol) and tetrahydrofuran (THF, 12.5 mL) followed by isopropoxypinacolborane (2.660 g, 14.3 mmol). The resulting solution is then cooled to 78 C. and a previously prepared lithium diisopropylamide solution (LDA, 13.32 mmol in 12.5 mL THF) is added dropwise. The reaction mixture is left to stir 1 h at 78 C. and is then allowed to warm to room temperature and stir for 1 hour at room temperature. After that time the reaction mixture is poured in 50 mL of HCl 2N and extracted with tert-butyl-methyl ether (TBME, 235 mL). The combined organic layers are washed with 50 mL water and 50 mL brine, then dried over sodium sulphate, filtered and the solvent is evaporated on rotary evaporator. The crude is then recrystallised from warm diisopropylether, filtered, and the obtained crystals are then washed with diisopropylether and dried under vacuum to obtain the pure product 129 (beige crystals, 2.420 g, yield: 73%).

(97) NMR: .sup.1H (400.1 MHz, CDCl.sub.3), =8.79 (1H, s), 8.55 (1H, s), 8.01 (1H, s), 4.03 (3H, s), 1.39 (24H, s).

(98) ##STR00149##

(99) d) The synthesis of 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-decyltetradecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione 130 is, for example, described in Lee, J.; Cho, S.; Yang, C.; J. Mater. Chem., 2011, 21, 8528-8531.

(100) In a 200 mL flask equipped with a condenser, a mechanical stirrer, an argon inlet and a thermometer is introduced the bis-boronic ester 129 (400 mg, 0.800 mmol) and 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-decyltetradecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione 130 (862 mg, 0.762 mmol). The flask is flushed with argon and dry THF (40 mL) is added by syringe. The resulting red solution is heated to reflux and a previously prepared solution of palladium(II) acetate (5.1 mg, 0.023 mmol) and 2-(di-tert-butylphosphino)-1-phenylpyrrole (26.2 mg, 0.091 mmol) in 10 mL THF is added at 60 C. The resulting mixture is stirred for 5 minutes at reflux temperature. After that time finely crushed lithium hydroxide monohydrate (201 mg, 4.80 mmol) is added in a single portion at 60 C. and is stirred at reflux temperature for 2.5 hours. After that time, the heating is stopped and the mixture is poured in methanol (400 mL) to precipitate the product. The polymer is filtered, and washed with water. The filtered solid is then put in a flask containing 150 mL chloroform and 150 mL of a 3% sodium cyanide aqueous solution and is heated under vigorous stirring at 55 C. for 4 h. The phases are separated and the organic phase is washed with water (3100 mL). Chloroform is then evaporated, and methanol is added to precipitate the product, which is filtered on a Bchner funnel, washed with water (200 mL) and methanol (50 mL) and dried in the oven. The treatment with sodium cyanide is then repeated a second time. The dried solid is then purified by soxhlet extraction, first with THF (200 mL, 4 h). The fraction soluble in tetrahydrofuran is discarded and the remaining solid is then subjected to soxhlet extraction with chloroform (200 mL, 8 h). The solution is concentrated, the product is precipitated in methanol, filtered and dried under reduced pressure to afford the polymer P-9 (812 mg, yield 82%). High temperature GPC: M.sub.w=83300, PD 2.98.

APPLICATION EXAMPLES

Photovoltaic Application of the Semiconducting Polymers

(101) The solar cell has the following structure: Al electrode/LiF layer/organic layer, including compound of the invention/[poly(3,4-ethylenedioxy-thiophene) (PEDOT)/poly(styrenesulfonic acid) (PSS)]/ITO electrode/glass substrate. The solar cells are made by spin coating a layer of the PEDOT-PSS on a pre-patterned ITO on glass substrate. Then a 1:X mixture of the semiconducting polymer (1% by weight): [70]PCBM (a substituted C.sub.70 fullerene) is spin coated (organic layer). LiF and Al are sublimed under high vacuum through a shadow-mask.

(102) Solar Cell Performance

(103) The solar cell is measured in homemade solar light simulator with Osram Xenon Short Arc XBO 450W lamp. Then with the External Quantum Efficiency (EQE) graph the current is estimated under AM1.5 conditions. The OPV performances of Semiconducting polymers are shown in the table below:

(104) TABLE-US-00002 Polymer:70PCBM Voc, Jsc, Example Polymer Solvent ratio V mA/cm.sup.2 FF, % , % 1 P-1 3-Methylthiophene/ 1:2 0.84 3.29 53.81 1.49 1-Methylnaphtalene (8:2) 2 P-2 CHCl.sub.3/oDCB.sup.1) (7:3) 1:2.5 0.76 14.20 44.94 4.74 3 P-3 3-Methylthiophene/ 1:2 0.82 9.50 62.98 4.87 1-Methylnaphtalene (8:2) 4 P-4 CHCl.sub.3/oDCB (8:2) 1:2 0.8 3.21 57.02 1.46 5 P-5 Xylene/Tetraline (9:1) 1:2 0.78 4.13 66.89 2.17 6 P-6 CHCl.sub.3/oDCB (8:2) 1:2 0.88 2.82 55.03 1.37 7 P-7 CHCl.sub.3/oDCB (8:2) 1:2 0.94 4.00 44.88 1.71 8 P-8 Xylene/Tetraline (8:2) 1:2 1.00 0.20 29.02 0.06 9 P-9 CHCl.sub.3/oDCB (8:2) 1:2 0.80 9.25 68.47 5.14 .sup.1)oDCB = ortho-dichlorobenzene.

(105) OFET Application of the Semiconducting Polymers:

(106) Semiconductor Film Deposition:

(107) Siliconwafers (Si n.sup.(42540 m)) with a 230 nm thick SiO.sub.2 dielectric and patterned indium tin oxide (15 nm)/gold (30 nm) contacts (L=20, 10, 5, 2.5 m, W=0.01 m; Fraunhofer IPMS (Dresden)) are prepared by standard cleaning by washing with acetone and i-propanol followed by oxygen plasma treatment for 30 minutes.

(108) The substrates are transferred in a glove box. An octyltrichlorsilane (OTS) monolayer is grown on the dielectric surface by putting the substrates in a 50 mM solution of octyltrichlorosilane (OTS) in trichloroethylene for 1 h. After monolayer growth, the substrates are washed with toluene to remove physisorbed silane.

(109) The semiconductor is dissolved in a proper solvent in a concentration 0.75% by weight at 80 C. and spin-coated at 1500 rpms for 60 s onto the substrates.

(110) OFET Measurement:

(111) OFET transfer and output characteristics are measured on an Agilent 4155C semiconductor parameter analyzer. The devices are annealed in a glovebox at 150 C. for 15 minutes before the measurements are done in a glove box under a nitrogen atmosphere at room temperature. For p-type transistors the gate voltage (V.sub.g) varies from 10 to 30 V and at drain voltage (V.sub.d) equal to 3 and 30V for the transfer characterisation. For the output characterization V.sub.d is varied from 0 to 30V at V.sub.g=0, 10, 20, 30 V.

(112) TABLE-US-00003 Mobility, Example Semiconductor Solvent cm.sup.2/Vs On/off 10 P-1 oDCB 8.90E04 7.20E+04 11 P-2 oDCB 5.90E03 5.10E+05 12 P-3 oDCB 3.70E03 4.50E+04 13 P-4 oDCB 1.40E03 1.60E+04 14 P-5 oDCB 1.50E03 1.60E+04 15 P-6 oDCB 3.40E03 1.10E+06 16 P-7 oDCB 3.60E03 3.1E+05 17 P-8 oDCB 3.10E08 4.50E+04 18 P-9 oDCB 2.10E02 8.8E+04

(113) When used in OPV cells, the polymers of the present invention show an improved short circuit voltage (Voc), while maintaining high short circuit current (Jsc) compared to polymers, wherein R.sup.1 and R.sup.2 are both hydrogen, or alkyl. The modifications of the benzodithiophene structure have a direct effect on Voc, as the introduction of electron withdrawing groups such as COOR.sup.301 or CN modifies the HOMO level of the polymer. This leads to improved efficiencies.

(114) As a comparison L. Huo et al. Macromolecules, 42 (2009) 6564-6571 obtained a V.sub.oc of 0.72 V and max. PCE of 4.45% with a polymer of formula

(115) ##STR00150##
(PDPPBDP) and 70PCBM., comprising a benzodithiophene repeating unit with R.sup.1R.sup.2=branched alkyl groups. Yuan et. al, Journal of Polymer Science Part A: Polymer Chemistry, 49 (2011) 701-711 obtained a maximum V.sub.oc of 0.76 V and PCE of 0.43% with

(116) ##STR00151##
(PBDPDPP) and 70PCBM.

(117) Another advantage of the polymers described in this invention is their very good solubility and film forming properties in common solvents, comprising non-halogenated solvents. Additionally, as R.sup.1 and R.sup.2 are not directly in the vicinity of the twistable bonds of the conjugated backbone the steric impact of modification of R.sup.301, R.sup.302, or R.sup.303 (on their respective functional group) on the electronic properties are very limited and in most cases inexistent. In other words, in the case R.sup.2=COOR.sup.301, for example, the solubility and film forming properties of the polymers can be independently adjusted by variations of the R.sup.301 group. Thus you can decouple the tuning of the electronic properties from the tuning of the film morphology which can be a decisive advantage in the development of such polymers. Finally, the variation of R.sup.301 and R.sup.303 in particular can be done at a late stage of the synthesis which helps expediting the development.