Polycyclic dithiophenes

Abstract

The present invention relates to novel compounds, corresponding oligomers and (co)polymers. The compounds according to the invention are useful as semiconductors and 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.

Claims

1. A compound of formula (I): ##STR00102## wherein: X is a divalent linking group selected from the group consisting of ##STR00103## R.sup.1 and R.sup.1 independently of each other are a substituent, a halogen or SiR.sup.6R.sup.4R.sup.5; R.sup.2 and R.sup.2 are optionally the same or different and are selected from the group consisting of hydrogen, a halogen, a C.sub.1-C.sub.25alkyl, a C.sub.7-C.sub.25arylalkyl or a C.sub.1-C.sub.25alkoxy, each of which is unsubstituted or substituted; R.sup.3 and R.sup.3 together with the carbon atoms to which they are attached, complete a 5- or 6-membered unsubstituted or substituted hydrocarbon ring having a structure: ##STR00104## Y and Y independently are selected from the group consisting of ##STR00105## n and p are both 0; R.sup.3 and R.sup.3 optionally together form a bridging group ##STR00106## R.sup.4, R.sup.5, R.sup.6 independently are a C.sub.1-C.sub.6alkyl; R.sup.7 and R.sup.7 independently represent H or the substituent, or vicinal R.sup.7 and R.sup.7, together with carbon atoms to which they are attached, complete a 5-membered unsubstituted or substituted heterocyclic ring comprising at least one heteroatom selected from the group consisting of N, O and S; R.sup.9, R.sup.9, R.sup.10 and R.sup.10 independently are hydrogen, wherein at least one of neighbouring residues R.sup.9 and R.sup.9, or R.sup.9 and R.sup.10, R.sup.9 and R.sup.10, or both, together with carbon atoms to which they are attached, complete a 5-membered unsubstituted or substituted heterocyclic ring comprising at least one heteroatom selected from the group consisting of N, O and S; the optional substituent is independently selected from the group consisting of a C.sub.1-C.sub.8alkyl, a hydroxyl group, a mercapto group, a C.sub.1-C.sub.8alkoxy, a C.sub.1-C.sub.8alkylthio, a halogen, a halo-C.sub.1-C.sub.8alkyl, a cyano group, a carbamoyl group, a nitro group and a silyl group; X.sup.5 is O or NR.sup.8; R.sup.8 and R.sup.8 are independently of each other hydrogen, a C.sub.6-C.sub.18aryl, a C.sub.6-C.sub.18aryl which is substituted by a C.sub.1-C.sub.18alkyl or a C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.25alkyl which may optionally be interrupted by one or more oxygen or sulfur atoms, or a C.sub.7C.sub.25arylalkyl; R.sup.51 and R.sup.51 are independently of each other hydrogen, a halogen, a C.sub.1-C.sub.25alkyl which may optionally be interrupted by one or more oxygen or sulfur atoms, a C.sub.6-C.sub.24aryl which may optionally be substituted one to three times with a C.sub.1-C.sub.8alkyl and/or a C.sub.1-C.sub.8alkoxy, a C.sub.7-C.sub.25arylalkyl, CN, or a C.sub.1-C.sub.25alkoxy, or R.sup.51 and R.sup.51 together form a ring; and R.sup.61 is H, a C.sub.1-C.sub.18alkyl which may optionally be interrupted by one or more oxygen or sulfur atoms, a C.sub.1-C.sub.18perfluoroalkyl, a C.sub.6-C.sub.24aryl which may optionally be substituted one to three times with a C.sub.1-C.sub.8alkyl and/or a C.sub.1-C.sub.8alkoxy, a C.sub.2-C.sub.20heteroaryl which may optionally be substituted one to three times with a C.sub.1-C.sub.8alkyl and/or a C.sub.1-C.sub.8alkoxy, or CN.

2. The compound of claim 1, wherein: R.sup.1 and R.sup.1 are independently of each other halogen or SiR.sup.6R.sup.4R.sup.5; R.sup.2 and R.sup.2 are optionally the same or different and are selected from the group consisting of halogen, hydrogen, a C.sub.1-C.sub.25alkyl, a C.sub.7-C.sub.25arylalkyl or a C.sub.1-C.sub.25alkoxy, each of which is unsubstituted or substituted; X is ##STR00107## wherein R.sup.3 and R.sup.3 together form the ring structure; R.sup.4, R.sup.5, R.sup.6 independently are a C.sub.1-C.sub.6alkyl; R.sup.9 R.sup.9, R.sup.10 and R.sup.10 independently are hydrogen; and the optional substituent is independently selected from the group consisting of a C.sub.1-C.sub.8alkyl, a hydroxyl group, a mercapto group, a C.sub.1-C.sub.8alkoxy, a C.sub.1-C.sub.8alkylthio, a halogen, a halo-C.sub.1-C.sub.8alkyl, a cyano group, a carbamoyl group, a nitro group and a silyl group.

3. The compound of claim 1, wherein: R.sup.1 and R.sup.1 are independently of each other halogen or SiR.sup.6R.sup.4R.sup.5; R.sup.2 and R.sup.2 are optionally the same or different and are selected from the group consisting of H, a C.sub.1-C.sub.25alkyl, a C.sub.7-C.sub.25arylalkyl or a C.sub.1-C.sub.25alkoxy; and R.sup.4, R.sup.5, R.sup.6 independently are a C.sub.1-C.sub.6alkyl.

4. A compound of formula (I): ##STR00108## wherein: X is a divalent linking group selected from the group consisting of ##STR00109## R.sup.1 and R.sup.1 are independently of each other H, halogen or SiR.sup.6R.sup.4R.sup.5; R.sup.2 and R.sup.2 independently are H or C.sub.1-C.sub.18alkyl; R.sup.3 and R.sup.3 together form a ring closing structure selected from the group consisting of SCHN, OCHN, and NRCHN, wherein a CH moiety is substituted, or ##STR00110## or R.sup.3 and R.sup.3 together form a bridging group: ##STR00111## R.sup.4, R.sup.5, R.sup.6 independently are C.sub.1-C.sub.8alkyl groups; n and p are 0; Y and Y independently are selected from the group consisting of ##STR00112## neighbouring residues R.sup.4 and R.sup.5 are optionally further interlinked to form a divalent hydrocarbon residue comprising 4 to 25 carbon atoms optionally substituted, interrupted, or both; R.sup.7 and R.sup.7 independently represent H or the substituent, or vicinal R.sup.7 and R.sup.7, together with carbon atoms to which they are attached, complete a 5-membered unsubstituted or substituted heterocyclic ring comprising at least one heteroatom selected from the group consisting of N, O, and S; R.sup.23 and R.sup.23 each represent an alkyl group, a hydroxyl or an alkoxy group; R.sup.8 is substituted phenyl; R.sup.9, R.sup.9, R.sup.10 and R.sup.10 independently are hydrogen and one or more of neighbouring residues R.sup.9 and R.sup.9 together form a moiety NCON whose nitrogen atoms are substituted, or R.sup.9 and R.sup.10, and R.sup.9 and R.sup.10 each, together with carbon atoms to which they are attached, complete an unsubstituted or substituted thienyl ring; q is 0, 1, 2, 3 or 4; R14, if present, is the substituent; the substituent, if present, is independently selected from the group consisting of a halogen, C.sub.1-C.sub.25alkyl, SiRRR, vinyl, allyl, and phenyl, and if bonding to a non-aromatic carbon or to a sulphur, the substituent is optionally oxo, wherein R, R, R independently are selected from the group consisting of C.sub.1-C.sub.8alkyl, and phenyl, and R is optionally a hydrogen, and each phenyl is unsubstituted or substituted by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, CHO, vinyl, allyl, allyloxy, acryloyloxy, methacryloyloxy, or halogen.

5. A semiconductor device, comprising the compound according to claim 1.

6. The semiconductor device of claim 5, comprising the compound of the formula (I) as a layer having a thickness from the range 5 to 1000 nm, on a rigid or flexible solid substrate.

7. An organic semiconductor material, layer or component, comprising the compound of claim 1.

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

9. An article, comprising the compound of claim 1, wherein the article is selected from the group consisting of a charge-transport material, a semiconducting material, an electrically conducting material, a photoconducting material, a light emitting material, a surface-modifying material, an electrode material in a battery, an alignment layer, an organic field effect transistor, an integrated circuit, a thin film transistor, a display, an RFID tag, an electro- or photoluminescent device, a backlight of a display, a photovoltaic or sensor device, a charge injection layer, a photodiode, a Schottky diode, a memory device, a planarising layer, an antistatic, a conductive substrate or pattern, a photoconductor, and an electrophotographic application or recording material.

10. The compound of claim 4, wherein q is 0.

Description

EXAMPLE 1

General Procedure for Suzuki Polymerization

(1) The starting material comprises a suitable ,-di(bromoaryl) monomer (1). In a three neck-flask, 0.71 g of potassium phosphate (K.sub.3PO.sub.4) dissolved in 2.1 ml of water (previously degassed with argon) is added to a degassed solution of 1.00 g of 1, an equivalent amount of the second monomer in form of a suitable ,-diboronic acid bis(1,3-propanediol)ester, 16.0 mg of tri-tert-butylphosphonium tetrafluoroborate ((t-Bu).sub.3P*HBF.sub.4) and 26.0 mg of tris(dibenzylideneacetone) dipalladium (0) (Pd.sub.2(dba).sub.3) in 10 ml of tetrahydrofuran. The reaction mixture is heated to 50 C. for approximately 13 hours. Subsequently, 18 mg bromo-thiophene and 20 minutes later 23 mg thiophene-boronic acid pinacol ester are added to stop the polymerisation reaction. The reaction mixture is cooled to room temperature and precipitated in methanol. The residue is purified by soxhiet extraction using pentane and the polymer is then extracted with cyclohexane and dried.

EXAMPLE 10

Synthesis of Building Block 17

(2) ##STR00065## a) 10 g 3 (obtained in analogy to example 11a below) are lithiated as described in Ex.11c (below) and then cooled to 78 C. 5 g solid carbon dioxide is added in one portion and the solution is allowed to warm to room temperature. The solution is again cooled to 0 C., quenched with diluted HCl and twice extracted with TBME. The combined organic phases are washed with brine, dried over sodium sulphate and evaporated to dryness. 50 ml acetic anhydride is added to the residue and the suspension is refluxed for 2 hours. After cooling down the slurry is extracted several times with hexane, the combined hexane phases are evaporated to dryness and further dried in a vacuum oven affording 7.4 g 16 as a reddish-white solid. b) The product from above is dissolved in THF, treated at 0 C. with 2.2 eq. hexylamine and stirred for 1 hour at room temperature. After standard work-up (TBME, diluted HCl, brine) the residue is suspended in acetic acid, treated with 10 eq. each of acetic anhydride and sodium acetate and refluxed for 16 hours. Then most of the solvent is evaporated and the residue is suspended in aqueous sodium bicarbonate, followed by extraction with TBME. The combined organic layers are washed with brine, dried and evaporated dryness affording 7.6 g 17 as a yellowish solid.

EXAMPLE 11

Synthesis of Building Block 26

(3) ##STR00066## a) A solution of 40 g of 22 in 200 ml of dry tetrahydrofuran (THF) is added rapidly to a solution of lithium diisopropylamide (LDA, prepared from 100 ml of 2.7 M solution of butyllithium in hexane and 28.8 g diisopropylamine in 200 ml of dry THF) at 70 C. under nitrogen atmosphere. After the colour of the mixture has become orange-brown, the mixture is allowed to warm to 20 C. and then 100 ml of water are added. The organic phase is separated, washed with brine, dried and evaporated. The residue is recrystallized from methanol to obtain 36.5 g of 4,4-dibromo-2,2-dithiophene as an off-white powder (yield: 91.2%).

(4) A solution of n-dodecyl magnesium bromide in ether (prepared from 9 g of magnesium turnings and 87.0 g n-dodecylbromide in 200 ml of diethylether) is slowly added to a solution of 40 g of 4,4-dibromo-2,2-dithiophene. 1 mol % NiCl.sub.2(dppp) (dppp=Ph.sub.2PCH.sub.2Ch.sub.2CH.sub.2PPh.sub.2) in 200 ml of diethylether is added in such a way, that the internal temperature does not exceed 20 C. Then the mixture is stirred at room temperature for 2 hours and 200 ml of water are added thereto. The organic phase is separated, washed with diluted hydrochloric acid and brine, dried and evaporated. The residue is suspended in methanol and 55.8 g of 4,4-n-didodecyl-2,2-dithiophene is obtained as a beige powder by filtation (yield: 70%). 12.8 g of bromine are added dropwise to a solution of 10.1 g 4,4-n-didodecyl-2,2-dithiophene in 100 ml chloroform and 40 ml acetic acid at 0 C. under nitrogen atmosphere. The mixture is heated at 60 C. for 16 hours. After cooling to room temperature the mixture is treated with 50 ml of a saturated solution of sodium sulfite. The organic phase is separated, washed with a saturated aqueous solution of sodium hydrogen carbonate and brine, dried and evaporated. The residue is suspended in methanol and 14.5 g of 23 is obtained as a beige powder by filtration. .sup.1H-NMR: (ppm) 0.89 (t, 6H), 1.27 (m, 36 H (18CH.sub.2)), 1.56 (m, 4H), 2.67 (dd, 4H); .sup.13C-NMR: (ppm) 14.51 (CH.sub.3), 23.08 (CH.sub.2), 28.93-32.31 (9CH.sub.2), 111.28 (C5), 114.82 (C3), 128.80 (C4), 141.68 (C2)

(5) ##STR00067## b) 10 g of 23 are dissolved in 150 ml dry THF and 70 ml heptane under nitrogen atmosphere and the solution is cooled to 20 C. After adding of 9.5 ml of a 2.7 M solution of butyllithium in heptane the obtained solution is stirred at 20 C. for 1 hour, 3 ml of trimethylsilyl chloride (TMSCI) is added thereto, the resulting mixture is stirred at 20 for 15 minutes and then allowed to warm to room temperature. After stirring for an additional hour 50 ml of water are added. The organic phase is separated, washed with brine, dried and evaporated to obtain 9.9 g of 24 as an orange-brown semisolid residue (yield: 100%).

(6) ##STR00068## c) Intermediate 24 is dissolved in 500 ml of dry THF under nitrogen atmosphere and the solution is cooled to 60 C. A 2.7 M solution of BuLi in heptane are added at once and the mixture is allowed to warm to 30 C. followed by addition of 11.5 ml dimethylcarbamyl chloride. After stirring at 20 C. for 15 minutes the mixture is allowed to warm to 0 C. and 100 ml of water are added thereto. The organic phase is separated, washed with brine, dried and evaporated to obtain 25 as a red residue (yield: 58%). .sup.1H-NMR: (ppm) 0.35 (s, 18 H), 0.90 (t, 6H), 1.28 (m, 36 H (18CH2)), 1.61 (m, 4H), 2.69 (dd, 4H); .sup.13C-NMR: (ppm) 0.00 (TMS), 13.72 (CH.sub.3), 22.23 (CH2), 28.95-31.52 (9CH.sub.2), 136.45, 142.98, 146.82, 152.40, 183.66 d) For the further reaction to 26, it is not necessary to isolate 25. The organic phase of c) is separated and washed with brine. 37.4 g of N-bromosuccinimide (NBS) are added thereto at 0 C., the mixture is stirred at 0 C. for 30 minutes and at room temperature for an additional hour. After evaporation the residue is washed with water and suspended in 200 ml of methanol. The mixture is heated under reflux for 1 hour and after cooling to room temperature. The product 26 is obtained as dark-violett flakes by filtation (yield: 55%). .sup.1H-NMR: (ppm) 0.88 (t, 6H), 1.26 (m, 36 H (18CH.sub.2)), 1.59 (m, 4H), 2.57 (dd, 4H) .sup.13C-NMR: (ppm) 14.50 (CH.sub.3), 23.09 (CH.sub.2), 29.40-32.31 (9CH.sub.2), 111.10 (CBr), 137.31, 139.78, 147.35, 182.13.

EXAMPLE 12

Synthesis of Building Block 27

(7) ##STR00069##

(8) 0.94 g of tetrakistriphenylphosphino palladium are added to a degassed solution of 11.13 g of 26 and 15.1 g of 2-(tributyltin)-thiophene in 100 ml of toluene and the mixture is heated under reflux for 16 h, cooled to room temperature and filtered through silica gel. The filtrate is evaporated, the residue is suspended in 100 ml of methanol, stirred for 1 hour and 10.5 g of the 3,5-didodecyl-2,6-di(thien-2-yl)-cyclopenta[2,1-b;3,4-b]dithiophen-4-one are obtained as dark-bluish solid by filtration (yield: 95%). .sup.1H-NMR: (ppm) 0.93 (t, 6H), 1.32 (m, 36 H (18CH.sub.2)), 1.65 (m, 4H), 2.83 (dd, 4H), 7.06 (m, 2H), 7.10 (m. 2H), 7.32 (dd, 2H). .sup.13C-NMR: (ppm) 14.51 (CH.sub.3), 23.08 (CH2), 28.60-32.31 (9CH.sub.2), 126.02, 126.32, 127.68, 134.15, 135.32, 141.04, 146.84, 184.20 (CO)

(9) 11.15 g of the preceding product are dissolved in 100 ml of THF and the solution is cooled to 0 C. 5.7 g NBS are added thereto, and the resulting mixture is stirred at 0 C. for 30 minutes and at room temperature for an additional hour. The solvent is evaporated, the residue is suspended in methanol and 13.0 g of 27 are obtained as dark-bluish solid by filtration (yield: 95%).

EXAMPLE 13

Synthesis of Building Block 28

(10) ##STR00070##

(11) Using 4-dodecyl-2-(tributyltin)-thiophene, the corresponding dialkylated variants 28 are obtained in an analogous procedure. .sup.1H-NMR: (ppm) 0.85 (2t, 12H), 1.1-1.4 (m, 40 H), 1.59 (m, 8H), 2.48 (dd, 8H), 7.77 (s, 2H)

EXAMPLE 14

Synthesis of Building Block 30

(12) ##STR00071## a) A solution of 24 in 150 ml of dry THF is cooled to 40 C. 16 ml of a 2.7 M solution of BuLi in heptane are added and the resulting solution is stirred at 20 C. for 15 minutes. 2.58 g of dimethyl dichloro silane are added thereto and the mixture is stirred at 0 C. for 30 minutes and at room temperature for an additional hour followed by adding of 50 ml of 1 N hydrochloric acid. The organic phase is separated, washed with brine, dried and evaporated to obtain 29 as colourless liquid (yield: 95%). b) Bromination using NBS in analogy to the method shown in example 11d yields 30.

EXAMPLE 15

Synthesis of Building Block 31

(13) ##STR00072##

(14) The same reaction sequence shown in example 12, but using the starting material 30 yielding in 31:

(15) .sup.41H-NMR: (ppm) 0.40 (s, 6H), 0.78 (t, 6H), 1.1-1.3 (m, 36H), 1.45 (m, 4H), 2.61 (dd, 4H), 6.73 (d, 2H), 6.87 (d, 2H) .sup.13C-NMR: (ppm) 0.00, 17.20, 25.77, 31-38 (tot. 20 C), 114.40, 127.95, 133.05, 133.50, 140.71, 147.83, 148.19, 149.58

EXAMPLE 16

Synthesis of Building Block 32

(16) ##STR00073##

(17) The same reaction sequence shown in example 14, but replacing dimethyl dichloro silane with the equivalent amount of diphenyl dichloro silane, gives 32 in 90% overall yield. .sup.13C-NMR: (ppm) 0.02, 17.30, 25.89, 31-38 (tot. 20 C), 111.186, 144.48, 147.95, 150.01

EXAMPLE 17

Synthesis of Building Block 33

(18) ##STR00074##

(19) In an analogous process (example 14 and 16), compound 33 can be synthesized.

(20) .sup.1H-NMR: (ppm) 0.34 (s, 18 H), 0.87 (t, 6H), 1.1-1.4 (m, 16H), 2.41 (dd, 4H), 7.3-7.4 (m, 8H), 7.65 (m, 2H). .sup.13C-NMR: (ppm) 0.00, 14.72, 23.15, 28.72, 29.31, 29.89, 31.56, 129.84, 135.02, 136.01, 141.08, 141.41, 155.18

EXAMPLE 18

Synthesis of Building Block 35

(21) ##STR00075## a) 34 is obtained as red powder (yield: 40%) according to example 12 with the exception that 3.20 g of 1,4-dimethylpiperazine-2,3-dione are used instead of dichlorodimethylsilane.

(22) .sup.1H-NMR: (ppm) 0.00 (s, 18H), 0.87 (t, 6H), 1.24 (m, 36 H (18CH.sub.2)), 1.62 (m, 4H), 2.57 (dd, 4H). .sup.13C-NMR: (ppm) 0.00 (TMS), 13.79 (CH.sub.3), 21.97 (CH2), 28.63-31.72 (10CH.sub.2), 136.45, 142.98, 146.82, 152.40, 174.83 b) Bromination using NBS in analogy to the method shown in example 11d yields 35.

EXAMPLE 19

Synthesis of Building Block 39

(23) ##STR00076## a) To a freshly prepared LDA solution (82 ml butyllithium [2.7 m in heptane], 22.6 g di-isopropyl amine and 300 ml dry THF) at 78 C. under a nitrogen atmosphere, a solution of 32.4 g 3,3-dibromo-2,2-dithiophene 36 in 150 ml of dry THF is slowly added. The solution is slowly warmed to 20 C., stirred for 15 minutes and then re-cooled to 78 C. 27.2 g trimethyl silylchloride is added at once and the solution is slowly allowed to warm to 0 C. After stirring for 1 hour at 0 C. the reaction mixture is quenched by adding 100 ml water. The phases are separated and the organic phase is washed twice with brine and dried over sodium sulphate. The residue is suspended in methanol and the formed solid is recovered by filtration and dried under vacuum. Affords 43 g (92%) of the title compound 37 as an off-white powder.

(24) .sup.1H-NMR: (ppm) 0.00 (s, 18 H), 6.81 (s, 2 H); .sup.13C-NMR: (ppm) 0.00 (TMS), 113.14 (C3), 134.11, 137.15, 143.05

(25) ##STR00077## b) 46.8 g 3,3-dibromo-5,5-di-trimethylsilyl-2,2-dithiophene 37 is dissolved in 500 ml of dry THF under a nitrogen atmosphere and cooled to 60 C. 78 ml butyl lithium (2.7 M in heptane) is added at once. The temperature rises to approximately 40 C. The dry ice bath is removed and the reaction mixture is slowly warmed to 30 C. At this point 11.5 ml dimethyl carbamoylchloride in 20 ml dry THF is added at once. The temperature rises to approximately 20 C. and the reaction mixture is stirred at that temperature for 15 minutes and then slowly warmed to 0 C. The reaction mixture is quenched by adding 100 ml water. The phases are separated and the organic phase is washed twice with brine and dried over sodium sulphate. Evaporation of the solvent affords 33.1 g of a red residue, which contains approximately 90% product 38 (NMR; corresponds to 88.5% yield). Purification can be achieved either by flash chromatography or suspension in methanol.

(26) .sup.1H-NMR: (ppm) 7.05 (s, 2H); .sup.13C-NMR: (ppm) 125.41 (C4), 141.08 (C2), 147.42 (C3), 152.21 (C5),180.51 (CO) c) The organic phase from reaction step b) can be directly used for the bromination step by adding 37.4 g N-bromo succinimide are added to the organic phase at once at 0 C. The reaction mixture is stirred for 30 minutes at 0 C. and 1 hour at room temperature. After evaporation to dryness the residue is washed twice with 200 ml water each, which is decanted, and then boiled for 1 hour in 200 ml methanol. After cooling to room temperature the product is collected by filtration. Affords 30.1 g (85.2%) of the title compound 39 as dark-violet flakes. .sup.1H-NMR: (ppm) 6.99 (s, 2H); .sup.13C-NMR: (ppm) 114.17 (C5), 124.62 (C4), 139.74 (C2), 148.80 (C3), 180.51 (CO)

EXAMPLE 20

Synthesis of Building Block 40

(27) ##STR00078##

(28) A solution of 9.37 g 3,3-dibromo-5,5-di-trimethylsilyl-2,2-dithiophene (37) in 150 ml dry THF is cooled to 40 C. 16 ml butyl lithium (2.7 M in heptane) are added at once and the resulting solution is stirred for 15 minutes at 20 C. 2.58 g dimethyl dichloro silane are added at once and the reaction mass is stirred for 30 minutes at 0 C. and 1 hour at room temperature. The reaction mixture is quenched by adding 50 ml 1 N HCl. The phases are separated and the organic phase is washed twice with brine and dried over sodium sulphate. Evaporation of the solvent affords 6.95 g (95% of th.) of the title compound 40 as colourless liquid, which is almost pure as determined by NMR. .sup.1H-NMR: (ppm) 0.00 (s, 18H), 0.08 (s, 6H), 6.83 (s, 2 H)

EXAMPLE 21

Synthesis of Building Blocks 42-46

(29) ##STR00079## a) A solution of 9.37 g 3,3-dibromo-5,5-di-trimethylsilyl-2,2-dithiophene (41) in 150 ml dry THF is cooled to 40 C. 16 ml butyl lithium (2.7 M in heptane) are added at once and the resulting solution is stirred for 15 minutes at 20 C. 3.20 g of 1,4-Dimethyl-piperazine-2,3-dione are added in one portion and the reaction mixture is allowed to warm to room temperature and stirred for an additional hour at this temperature. The reaction mixture is quenched by adding 50 ml 1 N HCl. The phases are separated and the organic phase is washed twice with brine and dried over sodium sulphate. Evaporation of the solvent affords a red residue, which is suspended in hexane. The obtained slurry is stirred for 1 hour and then filtered. The filter cake is washed with hexane and dried under vacuum. Affords 3.4 g (46% of th.) of the title compound 42 as a dark red powder. .sup.1H-NMR: (ppm) 0.00 (s, 18H), 7.23 (s, 2H); .sup.13C-NMR: (ppm) 0.00, 134.53, 136.08, 142.68, 148.47, 175.31

(30) ##STR00080## b) By reacting the above product 42 with o-diaminobenzene, the following compound 43 is obtained; using 1,2-diamino-4,5-di(2-ethylhexyloxy)-benzene instead of o-diaminobenzene yields 44. General procedure: 10 mmol 42 and 10 mmol of the aromatic ortho-diamine are dissolved in 50 ml of ethanol and refluxed for 2 hours. After cooling to 0 C. the yellow precipitate is filtered and washed with cold ethanol and dried in a vacuum oven affording the corresponding quinoxaline 43 or 44.

(31) NMR-spectrum of 43: .sup.1H-NMR: (ppm) 0.20 (s, 18H), 7.47 (dd, 2H), 7.94 (dd, 2H), 8.17 (s, 2H); .sup.13C-NMR: (ppm) 0.00, 129.08, 131.48, 135.64, 139.82, 140.01, 140.45, 141.26

(32) ##STR00081##

(33) To a solution of 43 or 44 in 100 ml THF, 2 equivalents of N-bromo-succinimide are added in one portion and the reaction mixture is heated to 40 C. and stirred at this temperature for 16 hours. The solvent is then evaporated and residue is washed several times with water and then recrystallized from ethanol. The corresponding quinoxaline 45 or 46 in 60-80% yield. NMR-spectrum of 46: .sup.1H-NMR: (ppm) 0.98 (t, 6H), 1.06 (t, 6H), 1.42 (m, 8H), 1.62 (m, 8H), 1.96 (m, 2H), 4.13 (d, 4H), 7.19 (s, 2H), 7.97 (s, 2H) .sup.13C-NMR: (ppm) 23.15, 24.09, 24.12, 29.18, 30.73, 30.74, 39.34, 71.58, 105.65, 112.51, 126.93, 133.24, 134.48, 135.53, 139.87, 154.10

EXAMPLE 22

Synthesis of Building Block 49

(34) ##STR00082## a) A solution of 0.5 g 25 in 5 ml THF is treated at 20 C. with 1.1 eq. butyl lithium and then slowly warmed to 0 C. The reaction is quenched by the addition of 1.1 eq. trifluoro acetic anhydride and stirred for an additional hour at room temperature.

(35) 10 ml tert.butylmethylether are added the the reaction mixture is washed with sodium bicarbonate and brine. The organic phase is separated and dried over sodium sulphate and evaporated to dryness. The residue is dissolved in 5 ml DMSO and 0.1 ml trifluoroacetic acid and stirred for 5 hours at 70 C., cooled down and poured onto a saturated sodium bicarbonate solution. The aqueous slurry is extracted twice with tert.butyl-methylether, the combined organic phases are washed with brine, dried over sodium sulphate and evaporated to dryness. Afford 0.35 g 47 as a greyish-white solid. b) A solution of the product from above in toluene is treated with 3 eq. Red-Al (1 M in THF) and stirred at 80 C. for 2 hours. After cooling down the reaction mixture is subsequently washed with diluted HCl and brine. The organic phase is dried over sodium sulphate and evaporated to dryness.

(36) The residue from above is dissolved in DMSO and, after the addition of 1.5 eq. butyl bromide, 5 eq. KOH and a catalytical amount of KI, stirred for 16 hours at room temperature. The reaction mass is poured onto diluted HCl and the aqueous slurry is extracted twice with hexane. The combined organic phases are washed with brine, dried over sodium sulphate and evaporated to dryness. The residue is further purified by flash chromatography affording 0.29 g 48 as a white solid. c) Bromination according to the method described in the last step of example 11d yields 49.

(37) .sup.1H-NMR: (ppm) 0.81 (2t, 12H), 0.9 (m, 4H), 1.1-1.3 (m, 46H), 1.48 (m, 4H), 1.78 (m, 4H), 2.63 (dd, 4H)

EXAMPLE 23

(38) ##STR00083##

(39) To 2.00 g (5.5 mmol) of 42 in 10 ml ethanol (abs) 1 ml (8.23 mmol) anisaldehyd and 2.17 g (27.42 mmol) ammoniumhydrocarbonate is added. The reaction mixture is heated at reflux under nitrogen overnight, cooled to 25 C., the product is filtered off and washed with ethanol (yield:1.66 g (63%)).

EXAMPLE 24

(40) ##STR00084##

(41) To 0.25 g (0.7 mmol) of 42 in 6 ml ethanol (abs) 0.11 g (1.0 mmol) benzaldehyde and 0.26 g (3.43 mol) ammonium acetate is added. The reaction mixture is heated at reflux under nitrogen overnight, cooled to 25 C., the products are filtered off and separated by column chromatography using a flash master (eluent heptane:ethyl acetate 5:1) (yield 51: 0.05 g (17%); yield 52: 0.24 g (83%)).

EXAMPLE 25

(42) ##STR00085##

(43) To 4.00 g (11.0 mmol) 42 in 80 ml acetic acid 2.23 g (12.1 mmol) 4-bromobenzaldehyde, 1.17 g (12.6 mmol) aniline and 3.38 g (43.9 mmol) ammonium acetate are added. The reaction mixture is stirred at 130 C. under nitrogen for 45 min., cooled to 25 C., and the product is filtered off and washed with AcOH/MeOH. (yield: 4.5 g (67.8%)).

EXAMPLE 26

(44) ##STR00086##

(45) 4 ml of 1.6M BuLi in hexane are added to 3 g (4.95 mmol) of the product of example 25 dissolved in 30 ml dry THF at 78 C. The reaction mixture is stirred for 1 h and 1.9 g (24.8 mmol) of dry DMF are added and allowed to warm to room temperature. The reaction is quenched with 0.5M HCl and the product is purified with column chromatography on silica gel with heptane:ethyl acetate (4:1) as an eluent (yield: 1.45 g (53%)).

EXAMPLE 27

(46) ##STR00087##

(47) 1.8 ml 1.6M BuLi in hexane (2.9 mmol) is added to 1 g of methyltriphenylphosphine bromide in 13 ml THF at 0 C. and stirred for 1 h. 1.13 g (2 mmol) of the product of example 26 in 5 ml THF is added and stirred for 1h at 0 C. Reaction mixture is wormed to RT and quenched with water. Product is extracted with ethyl acetated and purified by column chromatography with hexane:ethyl acetate as an eluent (yield: 0.81 g (73%)).

EXAMPLE 28

Synthesis of Polymer 101

(48) ##STR00088##

(49) 0.44 g of the product of example 27 and 0.025 g of 2,2-azobisisobutyronitrile (AlBN) are dissolved in 1.8 ml toluene, degassed and stirred at 80 C. for 24 h. The polymer is purified by multiple precipitation in methanol (yield: 0.29 g (65%); M.sub.W=22 000, PDI=3.1).

(50) HOMO=5.7 eV, LUMO=2.4 eV, QY=14%

EXAMPLE 29

(51) ##STR00089##

(52) 0.2g (0.53 mmol) of compound Y, 0.1 g (0.63 mmol) styrene boronic acid, 0.1 g (0.5 mmol) cupper (II) acetate and 200 mg of Molsieves 4A is stirred at 40 C. in CH2Cl2:pyridine for 3 days. Solvent is evaporated and product purified my column chromatography with heptane:ethylacetate (6:1) as en eluent. (Yield 41 mg (16%))

EXAMPLE 30

Synthesis of Polymer 102

(53) ##STR00090##

(54) 40 mg of product example 29 and 2 mg of 2,2-azobisisobutyronitrile (AlBN) are dissolved in 0.18 ml toluene, degassed and stirred at 80 C for 24 h. The polymer is purified by multiple precipitation in methanol (yield: 0.29 g (65%); Mw=27 600, PDI=2.8).

(55) LUMO=2.7 eV

EXAMPLE 31

Synthesis of Building Block 57

(56) ##STR00091##

(57) 1.82 g (5 mmol) of 42 (example 21) and 0.94 g (5 mmol) of 2-amino-4-bromoaniline is refluxed overnight in 10 ml Ethanol, cooled down to RT and product is filtered off. Yield 2.4 g (93%) of product 57.

EXAMPLE 32

Synthesis of Building Block 58

(58) ##STR00092##

(59) 2.4 g (4.65 mmol) of product 57, 0.93 g (6.97 mmol) potassium vinyltrifluoroborate, 0.42 g (0.465 mmol) tris(dibenzylideneacetone)dipalladium(0), 6.7 g (23.25 mmol) tri-t-butylphosphonium tetrafluoroborate are mixed in 20 ml THF, degassed and heated to 50 C. Degassed aqueous solution of potassium phosphate is added and reaction mixture is stirred at reflux for 3 h. Product is purified by column chromatography with hexane:ethyl acetate (1:20). Yield 1.3 g (59.1%) of product 58.

EXAMPLE 33

Synthesis of Polymer 103

(60) ##STR00093##

(61) 1 g of the product 58 of example 32 and 0.05 g of 2,2-azobisisobutyronitrile (AlBN) are dissolved in 5 ml toluene, degassed and stirred at 80 C. for 24 h. The polymer is purified by multiple precipitation in methanol (yield: 0.65 g (65%); M.sub.w=22 000, PDI=3.1).

(62) HOMO=5.7 eV, LUMO=3.0 eV

EXAMPLE 34

(63) ##STR00094##

(64) 10 mmol of 42 (example 21) and 10 mmol of the substituted 2-amino-aniline shown is refluxed for 2 hours in 50 ml Ethanol, cooled down to 0 C., and the yellow precipitate is filtered off, washed with cold ethanol and dried under vacuum, yielding product 59.

EXAMPLE 35

(65) ##STR00095##

(66) 10 g of the orthoquinone 42 and 10 g hydroxylamine are refluxed in 20 ml pyridine and 80 ml ethanol for 2 hours. The solvents are evaporated and the orange-red residue is suspended in 100 ml water for 3 hours. The product is isolated by filtration, extensively washed with water and dried in a vacuum oven affording 10.3 g 60 as a reddish-orange solid.

EXAMPLE 36

(67) ##STR00096##

(68) The product 60 as obtained in example 35 is suspended in 100 ml ethanol at 0 C. A solution of 25 g SnCl2 in 50 ml HCl conc. is added in one portion (exotherm). The reaction mixture is refluxed for 2-3 hours, cooled to 0 C. and filtered. The filter cake is washed with water and ethanol and suspended in 50 ml saturated aqueous NaHCO3 and 50 ml TBME. The organic phase is separated and washed with brine. Evaporation of the solvent affords 5.1 g 61 as beige powder.

(69) (if 1 N HCl (instead of HCl conc.) is used, the TMS-groups are not cleaved)

EXAMPLE 37

(70) ##STR00097##

(71) 1 g of diamine 61 and 1.4 g of triethylamine are dissolved in 10 ml methylene chloride at 0 C. 1.6 g thionyl chloride is added dropwise and the reaction mixture is stirred for 1 hour at room temperature and 5 hours at reflux. The reaction is quenched by adding 10 ml water and stirred for 30 minutes. The organic phase is separated and washed with water. After evaporation of the solvent the residue is purified by chromatography affording 0.45 g 63 as yellowish powder.

EXAMPLE 38

(72) 1 g of diamine 62 and 1 g orthoquinone 42 in 10 ml ethanol are refluxed for 4 hours. After cooling to 0 C. the yellow precipitate is filtered and washed with cold ethanol and dried in a vacuum oven affording quinoxaline 64 in 70% yield:

(73) ##STR00098##

(74) Several polymers can be synthesized using the above described building blocks using Suzuki polymerization conditions (Cf. Example 1).

(75) Therefore, all described building blocks containing a trimethyl-silyl protecting group such as 33, 40, 42, 50, 51, 52 and 53 can be transformed to the corresponding dibromide using similar conditions of example 11d. These corresponding dibromides and the already described dibromide 26, 27, 28, 30, 32, 35, 39, 45, 46 and 49 can used as monomers in combination with a bisboronic ester to form polymers claimed by this invention.

(76) All these dibromides themselves can be converted into bis boronic esters using known methods. These corresponding bis-boronic esters can then be used as momomers in combination of with the dibromides as described above to form polymers claimed by this invention.

(77) Examples for such polymers are those of the following examples 40 and 41.

EXAMPLE 39

(78) Compound 59 (example 34) is converted into the corresponding dibromo compound 65 in analogy to the method of example 21 (preparation of compounds 45 and 46).

EXAMPLE 40

(79) ##STR00099##

(80) In a three necked flask, 0.54 g of potassium phosphate (K.sub.3PO.sub.4) dissolved in 5 ml of water (previously degassed) is added to a degassed solution of 1.0 g of compound 65, 0.28 g of 2,5-thiopheneboronic acid bis(pinacol) ester, 11.7 mg of tri-tert-butylphosphonium tetrafluoroborate ((t-Bu).sub.3P*HBF.sub.4) and 23.3 mg of tris(dibenzylideneacetone) dipalladium (0) (Pd.sub.2(dba).sub.3) in 25 ml of tetrahydrofuran. The reaction mixture is heated at reflux temperature for two hours. Subsequently, 18 mg bromo-thiophene and, 20 minutes later, 24 mg of thiophene-boronic acid pinacol ester are added to stop the polymerisation reaction. The reaction mixture is cooled to room temperature and precipitated in methanol. The residue is purified by soxhlet extraction using pentane and cyclohexane and the polymer is then extracted with THF to give 0.62 g of a dark powder. Mw=19800, Polydispersity=1.6 (measured by HT-GPC).

EXAMPLE 41

(81) ##STR00100##

(82) In a three necked flask, 0.54 g of potassium phosphate (K.sub.3PO.sub.4) dissolved in 5 ml of water (previously degassed) is added to a degassed solution of 1.0 g of compound 65, 0.32 g of 4,7-bis-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-3,4-benzo[1,2,5]thiadiazole, 11.7 mg of tri-tert-butylphosphonium tetrafluoroborate ((t-Bu).sub.3P*HBF.sub.4) and 23.3 mg of tris(dibenzylideneacetone) dipalladium (0) (Pd.sub.2(dba).sub.3) in 25 ml of tetrahydrofuran. The reaction mixture is heated at reflux temperature for two hours. Subsequently, 18 mg bromothiophene and, 20 minutes later, 24 mg of thiophene-boronic acid pinacol ester are added to stop the polymerisation reaction. The reaction mixture is cooled to room temperature and precipitated in methanol. The residue is purified by soxhlet extraction using pentane and the polymer is then extracted with cyclohexan to give 0.81 g of a dark powder. Mw =18100, Polydispersity=1.6 (measured by HT-GPC).

EXAMPLE 42

(83) ##STR00101## a) 38.1 g of 66 are dissolved in 300 ml THF, the mixture is then cooled to <30 C. and 100 ml of Butyllithium (2.7M) are added. After stirring for 1 h at room temperature, the reaction mixture is cooled to 78 C., then 91.9 g Tri-n-butyltinchloride is added slowly. The reaction mixture is stirred for 2 hours at 78 C. and then heated to room temparture. The reaction mixture is then poured into an mixture of hydrochloric acid/ ice; the aqueous slurry is extracted twice with tert.butyl-methylether, the combined organic phases are washed with brine, dried over sodium sulphate and evaporated to dryness, affording 67 in good yield. b) 10 g of 67 and 4.26 g of 2,3-dibromo-2,3-dihydro-1,4-naphthoquinone are mixed in 100 ml toluene and the solution is degassed. 0.2 g of tris(dibenzylideneacetone) dipalladium(0) and 0.14 g of triphenylarsine are added. The reaction mixture is heated to 120 C. overnight. The reaction mixture is then filtered over silicagel, precipated in hexane and filtered, to obtain 68 in good yield.

EXAMPLE 43

Organic Field Effect Transistor (OFET)

(84) Bottom-gate thin film transistor (TFT) structures with p-Si gate (10 cm) are used for all experiments. A high-quality thermal SiO.sub.2 layer of 300 nm thickness serves as gate-insulator of C.sub.i=32.6 nF/cm.sup.2 capacitance per unit area. Source and drain electrodes are patterned by photolithography directly on the gate-oxide. Gold source drain electrodes defining channels of width W=10 mm and varying lengths L=4, 8, 15, 30 m are used. Prior to deposition of the organic semiconductor the SiO.sub.2 surface is derivatized either with hexadimethylsilazane (HMDS) by exposing to a saturated silane vapour at 160 C. for 2 hours or by spin coating the HMDS at a spinning speed of 800 rpm (rounds per minute) for about a minute, or by treating the substrate at 60 C. with a 0.1 M solution of octadecyltrichlorosilane (OTS) in toluene for 20 minutes. After rinsing with iso-propanol the substrates are dried.

(85) The semiconductor thin film is prepared either by spin-coating or drop casting the compound as identified in the following table in a 0.5% (w/w) solution in ortho-dichlorobenzene. The spin coating is accomplished at a spinning speed of 1000 rpm (rounds per minute) for about 60 seconds in ambient conditions. The devices are evaluated as-deposited and after drying at 120 C. for 15 minutes.

(86) The transistor performance is measured on an automated transistor prober (TP-10). From a linear fit to the square root of the saturated transfer characteristics, field effect mobility and on/off current ratio are determined. Characteristic data are compiled in the following table.

(87) TABLE-US-00001 TABLE OFET Characteristics Sample Field Effect On/off Threshold Compound Mobility Current Ratio Voltage 104 2.1 10.sup.3 cm.sup.2/Vs 1.8 10.sup.5 12 V 105 1.6 10.sup.4 cm.sup.2/Vs 5.3 10.sup.5 8 V