WO2012017005A2 - Polymers based on benzodiones - Google Patents

Polymers based on benzodiones Download PDF

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Publication number
WO2012017005A2
WO2012017005A2 PCT/EP2011/063364 EP2011063364W WO2012017005A2 WO 2012017005 A2 WO2012017005 A2 WO 2012017005A2 EP 2011063364 W EP2011063364 W EP 2011063364W WO 2012017005 A2 WO2012017005 A2 WO 2012017005A2
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substituted
group
independently
hydrogen
c2salkyl
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PCT/EP2011/063364
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French (fr)
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WO2012017005A3 (en
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Bernd Tieke
Kai Zhang
Pascal Hayoz
Mathias DÜGGELI
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/101—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an anthracene dye
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/124—Copolymers alternating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/312—Non-condensed aromatic systems, e.g. benzene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
    • C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3242—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more oxygen atoms as the only heteroatom, e.g. benzofuran
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/91—Photovoltaic applications
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/92—TFT applications
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to polymers comprising one or more (repeating) unit(s) of the formula I, and their use as organic semiconductor in organic devices, especially in organic photovoltaics (solar cells) and photodiodes, or in a device containing a diode and/or an organic field effect transistor.
  • the polymers according to the invention have excellent solubility in organic solvents and excellent film-forming properties.
  • 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.
  • T 1 and T 2 are a group Experimental details can be found in C. W. Greenhalgh et al., Dyes and Pigments 1 (1980) 103.
  • EP1344788A1 relates to polymer compounds comprising dibenzofurane, or dibenzo thio- phene repeating units
  • EP0436940A1 discloses a process for the production of benzodifurane compounds of for-
  • R and R' are independently of each other a naphthyl group, or an unsubstituted or substituted phenyl group.
  • U 1 is O, S, or NR 1 ;
  • U 2 is O, S, or NR 2 ;
  • T 1 and T 2 are independently of each other hydrogen, halogen, hydroxyl, cyano, -COOR 103 , - OCOR 103 , -NR 11 COR 103 , -CONR 11 R 113 , -OR 103' , -SR 103' , -SOR 103' , -S0 2 R 103' , - NR 112 S0 2 R 103' , -NR 112 R 113 , Ci-C 2 5alkyl, which may be substituted by E and/or interrupted by D, C5-Ci2cycloalkyl, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; C7-C2sarylalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2- C2oheteroaryl, or C2-C2oheteroaryl which is substituted by G;
  • R 1 and R 2 may be the same or different and are selected from hydrogen, a Ci-Ciooalkyl group, -COOR 103 , -COR 103 , a Ci-Ciooalkyl group which is substituted by one or more halogen atoms, hydroxyl groups, nitro groups, -CN, or C6-Ci8aryl groups and/or interrupted by - 0-, -COO-, -OCO-, or -S-; a C7-Ciooarylalkyl group, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; a carbamoyl group, C5-Ci2cycloalkyl, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; a C6-C2 4 aryl group, in particular phenyl or 1- or 2-naphthyl, which can be substituted one
  • R 103 and R 103' are independently of each other Ci-Ciooalkyl, especially C3-C2salkyl, Ci- C25alkyl substituted by E and/or interrupted by D, C7-C2sarylalkyl, C6-C2 4 aryl, C6-C2 4 aryl which is substituted by G, C2-C2oheteroaryl, or C2-C2oheteroaryl which is substituted by G, Ar 2 , Ar 2' , Ar 3 , Ar 3' , Ar 4 and Ar 4' have the meaning of Ar 1 , or are independently of each other Ci-Ciooalkyl, especially C3-C2salkyl, Ci- C25alkyl substituted by E and/or interrupted by D, C7-C2sarylalkyl, C6-C2 4 aryl, C6-C2 4 aryl which is substituted by G, C2-C2oheteroaryl, or C2-C2ohetero
  • R 3 and R 3' are independently of each other hydrogen, halogen, halogenated Ci-C2salkyl, especially CF 3 , cyano, Ci-C2salkyl, especially C 3 -C25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C7-C2sarylalkyl, or Ci-C2salkoxy;
  • R 104 and R 104' are independently of each other hydrogen, cyano, COOR 103 , or a Ci-C2salkyl group,
  • R 4 , R 4 ', R 5 , R 5 ', R 6 and R 6' are independently of each other hydrogen, halogen, halogenated Ci-C25alkyl, especially CF 3 , cyano, Ci-C2salkyl, especially C 3 -C2salkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C7-C2sarylalkyl, or Ci-C2salkoxy; R 114 is Ci-C25alkyl, especially C 3 -C2salkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms,
  • R 7 , R 7 ', R 9 and R 9' are independently of each other hydrogen, Ci-C2salkyl, especially C 3 - C25alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms; or C7-C25arylalkyl,
  • R 8 and R 8' are independently of each other hydrogen, C6-Ci8aryl; C6-Ci8aryl which is substituted by Ci-Ciealkyl, or Ci-Ciealkoxy; or Ci-C2salkyl, especially C 3 -C2salkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C7-C2sarylalkyl, R 11 and R 11 ' are independently of each other Ci-C2salkyl group, especially a Ci-Cealkyl group, C7-C25arylalkyl, or a phenyl group, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy;
  • R 12 and R 12' are independently of each other hydrogen, halogen, cyano, Ci-C2salkyl, especially C 3 -C25alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, Ci-C25alkoxy, C7-C25arylalkyl, or ⁇ , wherein R 13 is a Ci-Cioalkyl group, or a tri(Ci-C8alkyl)silyl group;
  • R 105 , R 105' , R 106 and R 106' are independently of each other hydrogen, halogen, cyano, Ci- C25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C7-C25arylalkyl, or Ci-Ciealkoxy,
  • R 107 is hydrogen, C7-C2sarylalkyl, C6-Ci8aryl; C6-Ci8aryl which is substituted by Ci-Ciealkyl, or Ci-Ciealkoxy; Ci-Ci8perfluoroalkyl; Ci-C2salkyl; especially C3-C2salkyl, which may be interrupted by -0-, or -S-; or -COOR 103 ; R 103 is is as defined above;
  • R 108 and R 109 are independently of each other H, Ci-C2salkyl, Ci-C2salkyl which is substituted by E and/or interrupted by D, C7-C2sarylalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C2oheteroaryl, C2-C2oheteroaryl which is substituted by G, C2-Ci8alkenyl, C2- Ciealkynyl, Ci-Ciealkoxy, Ci-Ciealkoxy which is substituted by E and/or interrupted by D, or C7-C25aralkyl, or
  • R 110 and R 111 are independently of each other H, Ci-Ciealkyl, Ci-Ciealkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6-C24aryl which is substituted by G, or C2- C2oheteroaryl, or C2-C2oheteroaryl which is substituted by G, or
  • R 108 and R 109 together form a five or six membered ring, which optionally can be substituted by Ci-Ciealkyl, Ci-Ciealkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6- C24aryl which is substituted by G, C2-C2oheteroaryl, C2-C2oheteroaryl which is substituted by G, C2-Ci8alkenyl, C2-Ci8alkynyl, Ci-Ciealkoxy, Ci-Ciealkoxy which is substituted by E and/or interrupted by D, or C7-C2saralkyl,
  • D is -CO-, -COO-, -S-, -0-, or -N R112-,
  • E is Ci-C 8 thioalkoxy, Ci-C 8 alkoxy, CN, -NR ⁇ Rm, -CONR 112 R 113 , or halogen,
  • G is E, or Ci-Ciealkyl
  • R 112 and R 113 are independently of each other H; C6-Ci8aryl; C6-Ci8aryl which is substituted by Ci-Ciealkyl, or Ci-Ciealkoxy; Ci-Ciealkyl; or Ci-Ciealkyl which is interrupted by -0-.
  • the polymer of the present invention, or an organic semiconductor material, layer or component, comprising the polymer of the present invention can be used in organic photovoltaics (solar cells) and photodiodes, or in an organic field effect transistor (OFET).
  • polymer comprises oligomers as well as polymers.
  • the oligomers of this invention have a weight average molecular weight of ⁇ 4,000 Daltons.
  • the polymers of this invention preferably have a weight average molecular weight of 4,000 Daltons or greater, especially
  • the polymers of this invention preferably have a polydispersity of 1.01 to 10, more preferably
  • the polymers of the present invention are preferably conjugated.
  • n is usually in the range of 4 to 1000, especially 4 to 200, very especially 5 to 150.
  • U 1 is preferably O or NR 1 ; more preferably NR 1 .
  • U 2 is preferably O or NR 1 ; more preferably NR 1 .
  • T 1 and T 2 are independently of each other hydrogen, halogen, cyano, - COOR 103 , -OCOR 103 , -OR 103 , -SR 103 , or Ci-C 2 5alkyl, which may be substituted by E and/or interrupted by D; more preferably hydrogen, halogen, cyano, -OR 103 , Ci-C2salkyl.
  • Most preferred T 1 and T 2 are hydrogen, or Ci-C2salkyl, especially hydrogen.
  • R 1 and R 2 may be different, but are preferably the same; and are preferably selected from hydrogen, a Ci-Ciooalkyl group, a Ci-Ciooalkyl group which is substituted by one or more halogen atoms, -CN, or C6-Ci8aryl groups and/or interrupted by -0-, -COO-, -OCO-, or -S-; a C7-C24arylalkyl group, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; and pentafluorophenyl.
  • R 1 and R 2 are selected from hydrogen, a Ci-C38alkyl group, a Ci-C38alkyl group which is substituted by one or more halogen atoms; a C7-C2sarylalkyl group, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; and pentafluorophenyl. Still more preferably R 1 and R 2 are selected from hydrogen and a Ci-C38alkyl group. Most preferred R 1 and R 2 are a Ci-C38alkyl group such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.
  • n-butyl isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, 1 ,1 ,3,3-tetramethylpentyl, n- hexyl, 1 -methyl hexyl, 1 ,1 ,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3- tetramethyl butyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2- ethylhexyl, n-nonyl, decyl, undecyl, especially n-dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, 2-eth
  • the groups R 1 and R 2 can be represented by formula
  • Chiral side chains such as R 1 and R 2 , can either be enantiomerically pure, homochiral, or racemic, which can influence the morphology of the polymers.
  • R 103 and R 103' are independently of each other Ci-C2salkyl, Ci-C2salkyl substituted by halogen, especially CF 3 , C7-C2sarylalkyl, or phenyl; more preferably Ci-C2salkyl.
  • Ar 2 , Ar 2' , Ar 3 , Ar 3' , Ar 4 and Ar 4' are independently of each other a group of formula (Xa), (Xb), (Xc), (Xd), (Xe), (Xg), (Xh), (Xk), (XI), (Xm), (Xn), (Xo), (Xp), (Xv), (Xx), (Xy), (Xz), (XIa), (Xlb), (Xlc), (Xld), (Xle), (Xlf), (Xlg), (Xlh), (Xli), (XII), or (Xlm); more preferably a group of formula (Xa), (Xc), (Xg), (Xh), (Xm), (Xn), (Xo), (Xp), (Xy), (Xle), (Xlf), (XII), or (Xlm), still more preferably a group of formula (Xa), (Xm), (Xn), (Xo), or (Xlm), still more
  • R 3 and R 3' are independently of each other hydrogen, halogen, CF3, cyano, Ci- C25alkyl or Ci-C2salkoxy; more preferably CF3, cyano or Ci-C2salkyl; most preferred hydrogen, or Ci-C25alkyl.
  • R 104 and R 104' are independently of each other hydrogen, cyano or a Ci-C2salkyl group, more preferably hydrogen, or a Ci-C2salkyl group, most preferred hydrogen.
  • R 4 , R 4 ', R 5 , R 5 ', R 6 and R 6' are independently of each other hydrogen, halogen, CF3, cyano, Ci-C2salkyl or Ci-C2salkoxy, more preferably hydrogen, CF3, cyano or Ci- C25alkyl; most preferred hydrogen, or Ci-C2salkyl.
  • R 7 , R 7' , R 9 and R 9' are independently of each other hydrogen, Ci-C2salkyl, more preferably C4-C2salkyl.
  • R 8 and R 8' are independently of each other hydrogen, Ci-C2salkyl, Ci-C2salkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or
  • C7-C25arylalkyl more preferably hydrogen, or Ci-C2salkyl.
  • R 11 and R 11 ' are independently of each other a Ci-C2salkyl group, especially a Ci-Cealkyl group, or phenyl; more preferably a Ci-Cealkyl group.
  • R 12 and R 12' are independently of each other hydrogen, Ci-C2salkyl, Ci-
  • R 13 is a Ci-Cioalkyl group, or a tri(Ci-C8alkyl)silyl group, more preferably hydrogen, Ci-C2salkyl, or Ci-C2salkoxy.
  • Ar 2 , Ar 2' , Ar 3 , Ar 3' , Ar 4 and Ar 4' have the meaning of Ar 1 , they are independently of each other a group of formula (XVa), (XVb), (XVc), (XVd) or (XVe), preferably a group of formula (XVa), (XVd) or (XVe), more preferably a group of formula (XVa).
  • R 105 , R 105' , R 106 and R 106' are independently of each other hydrogen, halogen, cyano, Ci-C2salkyl or Ci-Ciealkoxy, more preferably Ci-C2salkyl or Ci-Ciealkoxy, most pref- ered hydrogen, or Ci-C2salkyl.
  • R 107 is preferably hydrogen, Ci-C2salkyl, Ci-C2salkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C7-C2sarylalkyl, more preferably hydrogen, or Ci- C25alkyl, most preferred C4-C2salkyl.
  • R 108 and R 109 are independently of each other H, Ci-C2salkyl, Ci-C2salkyl which is substituted by E and/or interrupted by D, C7-C2sarylalkyl, C2-Ci8alkenyl, or C7-C2saralkyl, or R 108 and R 109 together form a five or six membered ring, which optionally can be substituted by Ci-Ciealkyl, Ci-Ciealkyl which is substituted by E and/or interrupted by D, C6- C 2 4aryl, C 6 -C 2 4aryl which is substituted by G, D is -CO-, -COO-, -S- or -0-, E is Ci- Cethioalkoxy, Ci-Cealkoxy, CN or halogen, G is E, or Ci-Ciealkyl.
  • R 108 and R 109 are independently of each other H, Ci-C2salkyl or C7-C2sarylalkyl. Most preferred R 108 and R 109 are independently of each other H, or Ci-C2salkyl.
  • D is preferably -CO-, -COO-, -S- or -0-, more preferably -COO-, -S- or -0-, most preferred - S- or -0-.
  • E is Ci-Cethioalkoxy, Ci-Cealkoxy, CN, or halogen, more preferably Ci- Cealkoxy, CN, or halogen, most preferred halogen, especially F.
  • R 112 and R 113 are independently of each other H; Ci-Ciealkyl; or Ci-Ciealkyl which is interrupted by -O-, more preferably H, or Ci-Ciealkyl; most preferred Ci-Ciealkyl.
  • the present invention is directed to polymers comprising one or more (repeating) unit(s) of the formula
  • U 1 is O, S, or NR 1 ;
  • U 2 is O, S, or NR 2 ;
  • T 1 and T 2 are independently of each other hydrogen, halogen, hydroxyl, cyano, -COOR 103 , - OCOR 103 , -NR 11 COR 103 , -CONR 11 R 113 , -OR 103' , -SR 103' , -SOR 103' , -S0 2 R 103' , - NR 112 S0 2 R 103' , -NR 112 R 113 , Ci-C 2 5alkyl, which which may be substituted by E and/or inter- rupted by D, C5-Ci2cycloalkyl, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; C7-C2sarylalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2- C2oheteroaryl, or C2-C2oheteroaryl which is substituted by G;
  • R 1 and R 2 may be the same or different and are selected from hydrogen, a Ci-Ciooalkyl group, -COOR 103 , -COR 103 , a Ci-Ciooalkyl group which is substituted by one or more halo- gen atoms, hydroxyl groups, nitro groups, -CN, or C6-Ci8aryl groups and/or interrupted by - 0-, -COO-, -OCO-, or -S-; a C7-Ciooarylalkyl group, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; a carbamoyl group, C5-Ci2cycloalkyl, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; a C6-C2 4 aryl group, in particular phenyl or 1- or 2-naphthyl, which can be
  • a is 1 , 2, or 3, a' is 1 , 2, or 3; wherein Ar 1 and Ar 1' are independently of each other a group of formula (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg) or (XVh) (as defined in claim 1); and R 103 , R 103' , R 112 , R 113 , D, E and G are as defined above; or a polymer comprising one or more (repeating) unit(s) of the formula
  • Y is preferably a group of formula .
  • U 1 and U 2 may be different, but are preferably the same.
  • U 1 is preferably O or NR 1 ; more preferably NR 1 .
  • U 2 is preferably O or NR 1 ; more preferably NR 1 .
  • T 1 and T 2 may be different, but are preferably the same.
  • T 1 and T 2 are preferably independently of each other hydrogen, halogen, cyano, -COOR 103 , -OCOR 103 , -OR 103 , -SR 103 , Ci-C25alkyl, which may be substituted by E and/or interrupted by D; more preferably hydrogen, halogen, cyano, -OR 103 , Ci-C2salkyl; most preferred hydrogen, or Ci-C2salkyl, especially hydrogen.
  • R 1 and R 2 may be different, but are preferably the same.
  • R 1 and R 2 are selected from hydrogen, a Ci-Ciooalkyl group, a Ci-Ciooalkyl group which is substituted by one or more halogen atoms, -CN, or C6-Ci8aryl groups and/or interrupted by -O-, -COO-, -OCO-, or -S-; a C7-Ciooarylalkyl group, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; and pentafluorophenyl.
  • R 1 and R 2 are selected from hydrogen, a Ci-C38alkyl group, a Ci-C38alkyl group which is substituted by one or more halogen atoms; a C7-C24arylalkyl group, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; and pentafluorophenyl; most preferred R 1 and R 2 are selected from hydrogen, or a Ci-C38alkyl group; especially a Ci-C38alkyl group.
  • a and a' may be different, but are preferably the same, a and a' are preferably 1 , or 2, more preferably 1.
  • Ar 2 and Ar 2' may be different, but are preferably the same.
  • Ar 2 and Ar 2' are independently of each a group of formula (Xa), (Xb), (Xc), (Xd), (Xe), (Xg), (Xh), (Xk), (XI), (Xm), (Xn), (Xo), (Xp), (Xv), (Xx), (Xy), (Xz), (Xla), (Xlb), (Xlc), (Xld), (Xle), (Xlf), (Xlg), (Xlh), (Xli), (XII), or (Xlm) (as defined above).
  • Ar 2 and Ar 2' are a group of formula (Xa), (Xc), (Xg), (Xh), (Xm), (Xn), (Xo), (Xp), (Xy), (Xle), (Xlf) and (Xlm). Still more preferably Ar 2 and Ar 2' are a group of formula (Xa), (Xm), (Xn), (Xo) and (Xlm). Most preferred Ar 2 and Ar 2' are a group of formula (Xa), (Xm) and (Xn), especially (Xm). Ar 1 and Ar 1 ' may be different, but are preferably the same.
  • Ar 1 and Ar 1' are independently of each other a group of formula (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), or (XVh), preferably a group of formula (XVa), (XVb), (XVc), (XVd) or (XVe), more preferably a group of formula (XVa), (XVd) or (XVe), most preferably a group of formula (XVa).
  • the present invention is directed to polymers, comprising one or more (repeating) unit(s) of the formula
  • U 1 is O, or NR 1 ;
  • U 2 is O, or NR 2 ;
  • T 1 and T 2 are independently of each other hydrogen, or Ci-C2salkyl, especially hydrogen; R 1 and R 2 may be the same or different and are selected from a Ci-C38alkyl group, especially Ce-C36alkyl group;
  • Rio6 are independently of each other hydrogen or Ci-C2salkyl; and R 107 and R 107' are independently of each other hydrogen or Ci-C2salkyl, especially Ci- C25alkyl;
  • R 1 08 and R 1 °9 are independently of each other H, or Ci-C 2 5alkyl [Okay?].
  • U 1 and U 2 are the same.
  • T 1 and T 2 are the same.
  • the present invention is directed to polymers, comprising (repeat- ing) unit(s) of the formula (II), wherein
  • A is a repeating unit of formula (I), and -COM 1 - is a repeating unit, which has the meaning of Ar 2 , wherein Ar 2 are as defined
  • k is 1 , 1 is 1 , r is 0, or 1 , z is 0, or 1 , and
  • Ar 14 , Ar 15 , Ar 16 and Ar 17 are independently of each other a group of formula
  • R 14 , R 14' , R 17 and R 17' are independently of each other H, or a Ci-C2salkyl group, especially a C6-C25alkyl, which may optionally be interrupted by one or more oxygen atoms.
  • Examples of repeating units -COM 1 - are groups of formula (Xa) to (Xz), (Xla) to (Xln) and (XVa) to (XVh).
  • groups of formula (Xa), (Xb), (Xc), (Xg), (XI), (Xm), (Xn), (Xo), (Xle), (Xlf), (XII), (Xlm), (Xln), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf) and (XVg) are preferred, groups of formula (Xa), (Xg), (XI), (Xm), (Xle), (Xlf), (Xlm), (XVa), (XVb), (XVd), and (XVe), are more preferred, groups of formula (Xa), (XI), (Xm), (Xle), (Xlm), (XVa), (XVb), and (XVd) are still more preferred. Groups formula (Xa), (Xm) and (Xlm) are most preferred.
  • R 104 and R 104' preferably are independently of each other hydrogen, cyano or a Ci-C25alkyl group, and R 14 and R 14 are independently of each other H, or a Ci-C2salkyl group, especially a C6-C2salkyl, which may optionally be interrupted by one or more oxygen atoms.
  • the polymer is a copolymer, comprising
  • n is number which results in a molecular weight of 4,000 to 2,000,000 Daltons, more preferably 10,000 to 1 ,000,000 and most preferably 10,000 to 100,000 Daltons. n is usually in the range of 4 to 1000, especially 4 to 200, very especially 5 to 150.
  • the present invention is directed to polymers, wherein A is a
  • R 3 and R 3' are independently of each other hydrogen, or Ci-C25alky
  • R 104 and R 104' are independently of each other hydrogen, cyano or a Ci- C25alkyl group
  • R 14 and R 14 are independently of each other H, or a Ci-C2salkyl group, especially a C6-C2salkyl, which may optionally be interrupted by one or more oxygen atoms.
  • Preferred polymers are shown below:
  • n 4 to 1000, especially 4 to 200, very especially 5 to 100,
  • T 1 and T 2 are independently of each other hydrogen, or Ci-C2salkyl, especially hydrogen;
  • R 1 is a Ci-C38alkyl group, especially a Ce-C36alkyl group,
  • R3 is hydrogen, halogen, cyano, Ci-C2salkyl or Ci-C2salkoxy, especially hydrogen or Ci- C25alkyl;
  • R 105 and R 105 ' are independently of each other hydrogen, halogen, cyano, Ci-C2salkyl or Ci- C25alkoxy, especially hydrogen or Ci-C2salkyl;
  • R 106 and R 106 ' are independently of each other hydrogen or Ci-C2salkyl
  • R 108 and R 109 are independently of each other H, or Ci-C2salkyl.
  • n is usually in the range of 4 to 1000, especially 4 to 200, very especially 5 to 150.
  • the polymers of the present invention can comprise more than 2 different repeating units, such as, for example, repeating units A, B and D, which are different from each other. If the polymers comprise repeating units of the formul , they
  • A is a repeating unit of formula (I)
  • D * is a repeating unit -COM 1 -
  • B is a repeating unit -COM 1 -, or a repeating unit of formula (I); with the proviso that A, B and D * are different from each other.
  • Copolymers of formula VII can be obtained, for example, by the Suzuki reaction.
  • the condensation reaction of an aromatic boronate and a halogenide, especially a bromide, commonly referred to as the "Suzuki reaction" is tolerant of the presence of a variety of organic functional groups as reported by N. Miyaura and A. Suzuki in Chemical Reviews, Vol. 95, pp. 457-2483 (1995).
  • Preferred catalysts are 2-dicyclohexylphosphino-2',6'-di- alkoxybiphenyl/palladium(ll)acetates, tri-alykl-phosphonium salts/palladium (0) derivatives and tri-alkylphosphine/palladium (0) derivatives.
  • Especially preferred catalysts are 2- dicyclohexylphosphino-2',6'-di-methoxybiphenyl (sPhos)/palladium(ll)acetate and, tri-tert- butylphosphonium tetrafluoroborate ((t-Bu) 3 P * HBF4)/tris(dibenzylideneacetone) dipalla- dium (0) (Pd2(dba) 3 ) and tri-tert-butylphosphine (t-Bu) 3 P/tris(dibenzylideneacetone) dipalla- dium (0) (Pd2(dba) 3 ).
  • This reaction can be applied to preparing high molecular weight polymers and copolymers.
  • ⁇ 2 are independently of each other hydrogen, or a Ci- Cioalkyl group, especially -C(CH 3 ) 2 C(CH 3 ) 2 -, -CH 2 C(CH 3 ) 2 CH 2 -, or -C(CH 3 ) 2 CH 2 C(CH 3 ) 2 -, and Y 13 and Y 14 are independently of each other hydrogen, or a Ci-Cioalkyl group,
  • the reaction is typically conducted at about 0 °C to 180 °C in an aromatic hydrocarbon solvent such as toluene, xylene.
  • aromatic hydrocarbon solvent such as toluene, xylene.
  • Other solvents such as dimethylformamide, dioxane, dimethoxyethan and tetrahydrofuran can also be used alone, or in mixtures with an aromatic hydrocarbon.
  • An aqueous base preferably sodium carbonate or bicarbonate, potassium phosphate, potassium carbonate or bicarbonate is used as activation agent for the boronic acid, boronate and as the HBr scav- enger.
  • a polymerization reaction may take 0.2 to 100 hours.
  • Organic bases such as, for example, tetraalkylammonium hydroxide, and phase transfer catalysts, such as, for example TBAB, can promote the activity of the boron (see, for example, Leadbeater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 and references cited therein).
  • phase transfer catalysts such as, for example TBAB
  • Other variations of reaction conditions are given by T. I. Wallow and B. M. Novak in J. Org. Chem. 59 (1994) 5034-5037; and M. Remmers, M. Schulze, and G. Wegner in Macromol. Rapid Commun. 17 (1996) 239-252. Controll of molecular weight is possible by using either an excess of dibromide, diboronic acid, or diboronate, or a chain terminator.
  • a catalyst/ligand system comprising a palladium catalyst and an organic phosphine or phosphonium compound
  • the organic phosphine is a trisubstituted phosphine of formula (VI), or phosphonium salt thereof, wherein X" independently of Y" represents a nitrogen atom or a C-R 2" group and Y" independently of X" represents a nitrogen atom or a C-R 9" group, R 1" for each of the two R 1" groups independently of the other represents a radical selected from the group Ci-C24-alkyl, C3-C2o-cycloalkyl, which includes especially both monocyclic and also bi-and tri-cyclic cycloalkyi radicals, Cs-Cw-aryl, which includes especially the phenyl, naphthyl, fluorenyl radical, C2-Ci3-heteroaryl, wherein the number of hetero atoms, selected from the group N, O, S, may be from 1 to 2, wherein the two radicals R 1" may also be linked to one another,
  • radicals R 1" may themselves each be mono-or poly- substituted independently of one another by substituents selected from the group hydrogen, Ci-C2o-alkyl, C2-C2 0 -alkenyl, C3-C8-cycloalkyl, C2-Cg-hetero-alkyl, Cs-Cio-aryl, C2-C9- heteroaryl, wherein the number of hetero atoms from the group N, O, S may be from 1 to 4, Ci-C2o-alkoxy, Ci-Cio-haloalkyl, hydroxy, amino of the forms NH-(Ci-C2o-alkyl), NH-(C5-Cio- aryl), N(Ci-C 2 o-alkyl) 2 , N(Ci-C 20 -alkyl) (C 5 -Ci 0 -aryl), N(C 5 -Ci 0 -aryl) 2 , N(Ci
  • Preferred organic phosphines are selected from trisubstituted phosphines of formula
  • R 5" and R 6" together form a ring 2
  • R3" and R 4" together form a ring
  • Examples of preferred catalysts include the following compounds:
  • Pd(OAc)2 [palladium(ll) acetate], palladium(ll) chloride, palladium(ll) bromide, lithium tetra- chloropalladate(ll),
  • PdCl2(PR 3 )2 wherein PR 3 is a trisubstituted phosphine of formula VI; palladium(O) diallyl ether complexes, palladium(ll) nitrate,
  • PdCI 2 Pd 2 (dba) 3 , Pd(dba) 2 , Pd(OAc) 2 , or Pd(PR 3 ) 2 .
  • Pd 2 (dba) 3 and Pd(OAc) 2 are preferred.
  • the palladium catalyst is present in the reaction mixture in catalytic amounts.
  • catalytic amount refers to an amount that is clearly below one equivalent of the (het- ero)aromatic compound(s), preferably 0.001 to 5 mol-%, most preferably 0.001 to 1 mol-%, based on the equivalents of the (hetero)aromatic compound(s) used.
  • the amount of phosphines or phosphonium salts in the reaction mixture is preferably from 0.001 to 10 mol-%, most preferably 0.01 to 5 mol-%, based on the equivalents of the (het- ero)aromatic compound(s) used.
  • the preferred ratio of Pd:phosphine is 1 :4.
  • the base can be selected from all aqueous and nonaqueous bases and can be inorganic, or organic. It is preferable that at least 1.5 equivalents of said base per functional boron group is present in the reaction mixture.
  • Suitable bases are, for example, alkali and alkaline earth metal hydroxides, carboxylates, carbonates, fluorides and phosphates such as sodium and potassium hydroxide, acetate, carbonate, fluoride and phosphate or also metal alcoholates. It is also possible to use a mixture of bases.
  • the base is preferably a lithium salt, such as, for example, lithium alkoxides (such as, for example, lithium methoxide and lithium ethoxide), lithium hydroxide, carboxylate, carbonate, fluoride and/or phosphate.
  • the at present most preferred base is aqueous LiOHxh O (monohydrate of LiOH) and (wa- terfree) LiOH.
  • the reaction is typically conducted at about 0 °C to 180 °C, preferably from 20 to 160°C, more preferably from 40 to 140°C and most preferably from 40 to 120°C.
  • a polymerization reaction may take 0.1 , especially 0.2 to 100 hours.
  • the solvent is THF
  • the base is
  • the solvent is for example selected from toluene, xylenes, anisole, THF, 2- methyltetrahydrofuran, dioxane, chlorobenzene, fluorobenzene or solvent mixtures comprising one or more solvents like e.g. THF/toluene and optionally water. Most preferred is THF, or THF/water.
  • the polymerisation is carried out in presence of
  • polymerisation is carried out in presence of a te, or Pd2(dba) 3 (tris(dibenzylideneacetone)dipalladium(O)) and
  • the palladium catalyst is present in an amount of preferably about 0.5 mol-%, based on the equivalents of the (hetero)aromatic compound(s) used.
  • the amount of phosphines or phosphonium salts in the reaction mixture is preferably about 2 mol-%, based on the equivalents of the (hetero)aromatic compound(s) used.
  • the preferred ratio of Pd:phosphine is about 1 :4.
  • the polymerization reaction is conducted under inert conditions in the absence of oxygen. Nitrogen and more preferably argon are used as inert gases.
  • the process described in WO2010/136352 is suitable for large-scale applications, is readily accessible and convert starting materials to the respective polymers in high yield, with high purity and high selectivity.
  • the process can provide polymers having weight average molecular weights of at least 10,000, more preferably at least 20,000, most preferably at least 30,000.
  • the at present most preferred polymers have a weight average molecular weight of 30,000 to 80,000 Daltons.
  • Molecular weights are determined according to high- temperature gel permeation chromatography (HT-GPC) using polystyrene standards.
  • the polymers preferably have a polydispersibility of 1.01 to 10, more preferably 1.1 to 3.0, most preferred 1.5 to 2.5.
  • a monofunctional aryl halide or aryl boronate such as, for example,
  • the polymers of the present invention can also be sythesized by the Stille coupling (see, for example, Babudri et al, J. Mater. Chem., 2004, 14, 11-34; J. K. Stille, Angew. Chemie Int. Ed. Engl. 1986, 25, 508).
  • X 11 ' is a group -SnR 2 0 R208 R209 anc
  • the tin compounds and the halogen compounds are preferably introduced into one or more inert organic solvents and stirred at a temperature of from 0 to 200°C, preferably from 30 to 170°C for a period of from 1 hour to 200 hours, preferably from 5 hours to 150 hours.
  • the crude product can be purified by methods known to the person skilled in the art and appropriate for the respective polymer, for example repeated re-precipitation or even by dialysis.
  • Suitable organic solvents for the process described are, for example, ethers, for example diethyl ether, dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, dioxolane, diisopropyl ether and tert-butyl methyl ether, hydrocarbons, for example hexane, isohexane, heptane, cyclohexane, benzene, toluene and xylene, alcohols, for example methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, 1-butanol, 2-butanol and tert- butanol, ketones, for example acetone, ethyl methyl ketone and isobutyl methyl ketone, amides, for example dimethylformamide (DMF), dimethylacetamide and N- methylpyrrolidone, nitriles, for example
  • the polymers of the present invention can also be synthesized by the Negishi reaction using a zinc reagent A-(ZnX 12 )2, wherein X 12 is halogen and halides, and COM 1 - (X23) 2 , wherein X 2 3 is halogen or triflate, or using A-(X 2 3) 2 and COM 1 -(ZnX 2 3) 2 .
  • A-(ZnX 12 )2 wherein X 12 is halogen and halides
  • COM 1 - (X23) 2 wherein X 2 3 is halogen or triflate
  • A-(X 2 3) 2 and COM 1 -(ZnX 2 3) 2 Reference is, for example, made to E. Negishi et al., Heterocycles 18 (1982) 1 17-22.
  • the polymers of the present invention can also be synthesized by the Hiyama reaction using a organosilicon reagent A-(SiR 210 R 211 R 212 ) 2 , wherein R 1 °, R 2i i and R 1 are identical or different and are halogen, or Ci-C 6 alkyl, and COM 1 -(X 23 ) 2 , wherein X 23 is halogen or triflate, or using A-(X 2 3) 2 and COM 1 -(SiR 210 R 211 R 212 ) 2 .
  • a organosilicon reagent A-(SiR 210 R 211 R 212 ) 2 , wherein R 1 °, R 2i i and R 1 are identical or different and are halogen, or Ci-C 6 alkyl
  • COM 1 -(X 23 ) 2 wherein X 23 is halogen or triflate
  • Homopolymers of the type (A) n can be obtained via Yamamoto coupling of dihalides
  • X -A— X 10 the type (A) n can be obtained via oxidative polymerization of units where X 10 is hydrogen, e.g. with FeC as oxidizing agent.
  • (V) are intermediates in the production of the polymers of the present invention, are new and form a further subject of the present invention
  • a, a', b, b', c, c', d, d', Y, Ar 1 , Ar 1' , Ar 2 , Ar 2' , Ar 3 , Ar 3' , Ar 4 and Ar 4' are as defined in claim 1
  • X is halogen, especially Br, or J, ZnX 12 , - SnR ⁇ R ⁇ F ⁇ o g , wherein R 2 °7, R 2 oe and R 209 are identical or different and are H or Ci- Cealkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or unbranched and X 12 is a halogen atom, very especially I, or Br; or -
  • X is preferably different from a halogen atom.
  • T 1 and T 2 are independently of each other hydrogen, or Ci-C2salkyl, especially hydrogen;
  • R 1 is a Ci-C38alkyl group, especially a Ce-C36alkyl group,
  • R 105 and R 105' are independently of each other hydrogen, halogen, cyano, Ci-C2salkyl or Ci- C2 5 alkoxy, especially hydrogen or Ci-C2salkyl.
  • the polymers, wherein R 1 and/or R 2 are hydrogen can be obtained by using a protecting group which can be removed after polymerization.
  • a protecting group which can be removed after polymerization.
  • EP- A-0648770, EP-A-0648817, EP-A-0742255, EP-A-0761772, WO98/32802, W098/45757, WO98/58027, WO99/0151 1 , WOOO/17275, WOOO/39221 , WOOO/63297 and E P-A- 1086984 which describe the basic procedural method. Conversion of the pigment precursor into its pigmentary form is carried out by means of fragmentation under known conditions, for example thermally, optionally in the presence of an additional catalyst, for example the catalysts described in WOOO/36210.
  • L is preferably a group of formula or wherein Z 1 , Z 2 and Z 3 are independently of each other Ci-C 6 alkyl,
  • Z 4 and Z 8 are independently of each other Ci-C 6 alkyl, Ci-C 6 alkyl interrupted by oxygen, sulfur or N(Z 12 )2, or unsubstituted or Ci-C6alkyl-, Ci-C6alkoxy-, halo-, cyano- or nitro- substituted phenyl or biphenyl,
  • Z 5 , Z 6 and Z 7 are independently of each other hydrogen or Ci-C 6 alkyl
  • Z 9 is hydrogen, Ci-C 6 alkyl or a group of formula , or
  • Z 10 and Z 11 are each independently of the other hydrogen, Ci-C6alkyl, Ci-C6alkoxy, halogen, cyano, nitro, N(Z 12 )2, or unsubstituted or halo-, cyano-, nitro-, Ci-C6alkyl- or
  • Z 12 and Z 13 are Ci-C 6 alkyl
  • Z 14 is hydrogen or Ci-C 6 alkyl
  • Z 15 is hydrogen, Ci-C 6 alkyl, or unsubstituted or Ci-C6alkyl-substituted phenyl
  • Q * is p,q-C2-C6alkylene unsubstituted or mono- or poly-substituted by Ci-C6alkoxy, Ci-C6alkylthio or C2-Ci2dialkylamino, wherein p and q are different position numbers, X" is a hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, m' being the number 0 when X" is oxygen or sulfur and m being the number 1 when X" is nitrogen, and
  • L 1 and L 2 are independently of each other unsubstituted or mono- or poly-Ci-Ci2alkoxy-, -Ci-Ci2alkylthio-, -C2-C24dialkylamino-, -C6-Ci2aryloxy-, -C6-Ci2arylthio-,
  • Ci-C6alkyl -C7-C24alkylarylamino- or -Ci2-C24diarylamino-substituted Ci-C6alkyl or [-(p',q -
  • C2-C 6 alkylene)-Z-]n -Ci-C 6 alkyl n' being a number from 1 to 1000, p' and q' being different position numbers, each Z independently of any others being a hetero atom oxygen, sulfur or Ci-Ci2alkyl-substituted nitrogen, and it being possible for C2-C6alkylene in the repeating [-C2-C 6 alkylene-Z-] units to be the same or different,
  • Most preferred L is a
  • Halogen is fluorine, chlorine, bromine and iodine.
  • Ci-C25alkyl (Ci-Ciealkyl) is typically linear or branched, where possible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, 1 ,1 ,3,3-tetramethylpentyl, n-hexyl, 1 -methyl hexyl, 1 ,1 ,3,3,5,5- hexamethylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3-methyl- heptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2-ethylhexyl,
  • Ci-Cealkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl-propyl, n- hexyl, n-heptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2-ethylhexyl.
  • Ci-C4alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.-butyl.
  • C2-Ciealkenyl groups are straight-chain or branched alkenyl groups, such as e.g. vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2- enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.
  • alkenyl groups such as e.g. vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2- enyl, n-oct-2-enyl, n-dodec-2
  • C2-iealkynyl is straight-chain or branched and preferably C2-ealkynyl, which may be unsubstituted or substituted, such as, for example, ethynyl, 1-propyn-3-yl, 1-butyn-4-yl,
  • Ci-C25alkoxy groups are straight-chain or branched alkoxy groups, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecy- loxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy and octade- cyloxy.
  • Ci-Cealkoxy examples are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, 2,2-dimethylpropoxy, n-hexoxy, n-heptoxy, n-octoxy, 1 , 1 ,3,3-tetramethylbutoxy and 2-ethylhexoxy, preferably Ci- C 4 alkoxy such as typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy.
  • alkylthio group means the same groups as the alkoxy groups, except that the oxygen atom of the ether linkage is replaced by a sulfur atom.
  • Ci-Ci 8 perfluoroalkyl is a branched or unbranched radical such as for example -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF(CF 3 ) 2 , -(CF 2 ) 3 CF 3 , and -C(CF 3 ) 3 .
  • Carbamoyl group is typically a Ci-i8carbamoyl radical, preferably Ci-ecarbamoyl radical, which may be unsubstituted or substituted, such as, for example, carbamoyl, me- thylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, tert-butylcarbamoyl, dimethylcarbamoy- loxy, morpholinocarbamoyl or pyrrolidinocarbamoyl.
  • Ci-i8carbamoyl radical preferably Ci-ecarbamoyl radical, which may be unsubstituted or substituted, such as, for example, carbamoyl, me- thylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, tert-butylcarbamoyl, dimethylcar
  • C5-Ci2cycloalkyl is typically cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted or substituted.
  • the cycloalkyi group in particular a cyclohexyl group, can be condensed one or two times by phenyl which can be substituted one to three times with Ci-C 4 -alkyl, halogen and cyano. Examples of such condensed
  • R 155 and R 156 are independently of each other Ci-Ce-alkyl, Ci-Ce-alkoxy, halogen and cyano, in particular hydrogen.
  • C6-C2 4 aryl is typically phenyl, indenyl, azulenyl, naphthyl, biphenyl, as- indacenyl, s-indacenyl, acenaphthylenyl, fluorenyl, phenanthryl, fluoranthenyl, triphenlenyl, chrysenyl, naphthacen, picenyl, perylenyl, pentaphenyl, hexacenyl, pyrenyl, or anthracenyl, preferably phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, 9-phenanthryl, 2- or 9-fluorenyl, 3- or 4-biphenyl, which may be unsubstituted or substituted.
  • C6-Ci2aryl examples include phenyl, 1-naphthyl, 2-naphthyl, 3- or 4-biphenyl, 2- or 9-fluorenyl or 9-phenanthryl, which may be unsubstituted or substituted.
  • C7-C25aralkyl is typically benzyl, 2-benzyl-2-propyl, ⁇ -phenyl-ethyl, ⁇ , ⁇ -dimethylbenzyl, co-phenyl-butyl, ⁇ , ⁇ -dimethyl-co-phenyl-butyl, ⁇ -phenyl-dodecyl, ⁇ -phenyl-octadecyl, ⁇ -phenyl-eicosyl or ⁇ -phenyl-docosyl, preferably C7-Ci8aralkyl such as benzyl, 2-benzyl-2- propyl, ⁇ -phenyl-ethyl, ⁇ , ⁇ -dimethylbenzyl, co-phenyl-butyl, ⁇ , ⁇ -dimethyl-co-phenyl-butyl, ⁇ -phenyl-dodecyl or ⁇ -phenyl-octadecyl, and particularly preferred C7-Ci2
  • Heteroaryl is typically C2-C2oheteroaryl, i.e.
  • Possible substituents of the above-mentioned groups are Ci-Cealkyl, a hydroxyl group, a mercapto group, Ci-Cealkoxy, Ci-Cealkylthio, halogen, halo-Ci-Cealkyl, a cyano group, a carbamoyl group, a nitro group or a silyl group, especially Ci-Cealkyl, Ci-Cealkoxy, Ci- Cealkylthio, halogen, halo-Ci-Cealkyl, or a cyano group.
  • Ci-Ciealkyl interrupted by one or more O is, for example, (CH2CH20)i-g-R x , where R x is H or Ci-Ci 0 alkyl, CH 2 -CH(OR y ')-CH 2 -0-R y , where R y is Ci-Ci 8 alkyl, and R y ' embraces the same definitions as R y or is H.
  • a substituent such as, for example R 3 , occurs more than one time in a group, it can be different in each occurrence.
  • a mixture containing a polymer of the present invention results in a semi-conducting layer comprising a polymer of the present invention (typically 5% to 99.9999% by weight, especially 20 to 85 % by weight) and at least another material.
  • the other material can be, but is not restricted to a fraction of the same polymer of the present invention with different mo- lecular weight, another polymer of the present invention, a semi-conducting polymer, organic small molecules, carbon nanotubes, a fullerene derivative, inorganic particles (quantum dots, quantum rods, quantum tripods, T1O2, ZnO etc.), conductive particles (Au, Ag etc.), insulator materials like the ones described for the gate dielectric (PET, PS etc.).
  • the polymers of the present invention can be blended with small molecules described, for example, in WO2009/047104, PCT/EP2010/053655, WO09/047104, US6,690,029, WO2007082584, and WO2008107089:
  • X * is -0-, -S-, -Se- or -NR'"-,
  • R * is cyclic, straight-chain or branched alkyl or alkoxy having 1 to 20 C-atoms, or aryl having 2-30 C-atoms, all of which are optionally fluorinated or perfluorinated,
  • R' is H, F, CI, Br, I, CN, straight-chain or branched alkyl or alkoxy having 1 to 20 C-atoms and optionally being fluorinated or perfluorinated, optionally fluorinated or perfluorinated aryl having 6 to 30 C-atoms, or CO2R", with R" being H, optionally fluorinated alkyl having 1 to 20 C-atoms, or optionally fluorinated aryl having 2 to 30 C-atoms,
  • R'" is H or cyclic, straight-chain or branched alkyl with 1 to 10 C-atoms, y is 0, or 1 , x is 0, or 1.
  • the polymer can contain a small molecule, or a mixture of two, or more small molecule compounds. Accordingly, the present invention also relates to an organic semiconductor material, layer or component, comprising a polymer according to the present invention.
  • the polymers of the invention can be used as the semiconductor layer in semiconductor devices. Accordingly, the present invention also relates to semiconductor devices, comprising a polymer of the present invention, or an organic semiconductor material, layer or component.
  • the semiconductor device is especially an organic photovoltaic (PV) device (solar cell), a photodiode, or an organic field effect transistor.
  • PV organic photovoltaic
  • the polymers of the invention can be used alone or in combination as the organic semiconductor layer of the semiconductor device.
  • the layer can be provided by any useful means, such as, for example, vapor deposition (for materials with relatively low molecular weight) and printing techniques.
  • the compounds of the invention may be sufficiently solu- ble in organic solvents and can be solution deposited and patterned (for example, by spin coating, dip coating, ink jet printing, gravure printing, flexo printing, offset printing, screen printing, microcontact (wave)-printing, drop or zone casting, or other known techniques).
  • the polymers of the invention can be used in integrated circuits comprising a plurality of OTFTs, as well as in various electronic articles.
  • Such articles include, for example, radio- frequency identification (RFID) tags, backplanes for flexible displays (for use in, for example, personal computers, cell phones, or handheld devices), smart cards, memory devices, sensors (e.g. light-, image-, bio-, chemo-, mechanical- or temperature sensors), especially photodiodes, or security devices and the like.
  • RFID radio- frequency identification
  • a further aspect of the present invention is an organic semiconductor material, layer or component comprising one or more polymers of the present invention.
  • a further aspect is the use of the polymers or materials of the present invention in an organic photovoltaic (PV) device (solar cell), a photodiode, or an organic field effect transistor (OFET).
  • a further as- pect is an organic photovoltaic (PV) device (solar cell), a photodiode, or an organic field effect transistor (OFET) comprising a polymer or material of the present invention.
  • the polymers of the present invention are typically used as organic semiconductors in form of thin organic layers or films, preferably less than 30 microns thick.
  • the thickness may also be less than about 1 micron thick.
  • the layer thickness may typically be 100 nm or less. The exact thickness of the layer will depend, for example, upon the requirements of the electronic device in which the layer is used.
  • the active semiconductor channel between the drain and source in an OFET may comprise a layer of the present invention.
  • An OFET device preferably comprises:
  • the semiconductor layer comprises one or more polymers of the present invention.
  • the gate, source and drain electrodes and the insulating and semiconducting layer in the OFET device may be arranged in any sequence, provided that the source and drain elec- trade are separated from the gate electrode by the insulating layer, the gate electrode and the semiconductor layer both contact the insulating layer, and the source electrode and the drain electrode both contact the semiconducting layer.
  • the OFET comprises an insulator having a first side and a second side, a gate electrode located on the first side of the insulator, a layer comprising a polymer of the present invention located on the second side of the insulator, and a drain electrode and a source electrode located on the polymer layer.
  • the OFET device can be a top gate device or a bottom gate device.
  • the gate insulator layer may comprise for example a fluoropolymer, like e.g. the commer- cially available Cytop 809M®, or Cytop 107M® (from Asahi Glass).
  • a fluoropolymer like e.g. the commer- cially available Cytop 809M®, or Cytop 107M® (from Asahi Glass).
  • the gate insulator layer is deposited, e.g. by spin-coating, doctor blading, wire bar coating, spray or dip coating or other known methods, from a formulation comprising an insulator material and one or more solvents with one or more fluoro atoms (fluorosolvents), preferably a per- fluorosolvent.
  • a suitable perfluorosolvent is e.g. FC75® (available from Acros, catalogue number 12380).
  • fluoropolymers and fluorosolvents are known in prior art, like for example the perfluoropolymers Teflon AF® 1600 or 2400 (from DuPont), or Fluoro- pel® (from Cytonix) or the perfluorosolvent FC 43® (Acros, No. 12377).
  • the semiconducting layer comprising a polymer of the present invention may additionally comprise at least another material.
  • the other material can be, but is not restricted to another polymer of the present invention, a semi-conducting polymer, a polymeric binder, organic small molecules different from a polymer of the present invention, carbon nano- tubes, a fullerene derivative, inorganic particles (quantum dots, quantum rods, quantum tripods, T1O2, ZnO etc.), conductive particles (Au, Ag etc.), and insulator materials like the ones described for the gate dielectric (PET, PS etc.).
  • the semiconductive layer can also be composed of a mixture of one or more polymers of the present invention and a polymeric binder.
  • the ratio of the polymers of the present invention to the polymeric binder can vary from 5 to 95 percent.
  • the polymeric binder is a semicristalline polymer such as polystyrene (PS), high-density polyethylene (HDPE), polypropylene (PP) and polymethylmethacrylate (PMMA). With this technique, a degradation of the electrical performance can be avoided (cf. WO2008/001 123A1).
  • the polymers of the present invention are advantageously used in organic photovoltaic (PV) devices (solar cells). Accordingly, the invention provides PV devices comprising a polymer according to the present invention. A device of this construction will also have rectifying properties so may also be termed a photodiode. Photoresponsive devices have application as solar cells which generate electricity from light and as photodetectors which measure or detect light.
  • PV organic photovoltaic
  • PV device organic photovoltaic devices
  • the structure of organic photovoltaic devices is, for example, described in C. Deibel et al. Rep. Prog. Phys. 73 (2010) 096401 and Christoph Brabec, Energy Environ. Sci 2. (2009) 347-303.
  • the PV device comprise in this order:
  • transition layer such as an alkali halogenide, especially lithium fluoride
  • the photoactive layer comprises the polymers of the present invention.
  • the photoactive layer is made of a conjugated polymer of the present invention, as an electron donor and an acceptor material, like a fullerene, particularly a functionalized fullerene
  • the photoactive layer may also contain a polymeric binder.
  • the ratio of the polymers of formula I to the polymeric binder can vary from 5 to 95 percent.
  • the polymeric binder is a semicristalline polymer such as polystyrene (PS), high-density polyethylene (HDPE), polypropylene (PP) and polymethyl- methacrylate (PMMA).
  • the fullerenes useful in this in- vention may have a broad range of sizes (number of carbon atoms per molecule).
  • fullerene as used herein includes various cage-like molecules of pure carbon, including Buckminsterfullerene (C6o) and the related "spherical" fullerenes as well as carbon nano- tubes.
  • Fullerenes may be selected from those known in the art ranging from, for example, C2o-Ciooo- Preferably, the fullerene is selected from the range of C6o to C96. Most preferably the fullerene is C60 or C70, such as [60]PCBM, or [70]PCBM. It is also permissible to utilize chemically modified fullerenes, provided that the modified fullerene retains acceptor-type and electron mobility characteristics.
  • the acceptor material can also be a material selected from the group consisting of any semi-conducting polymer, such as, for example, a polymer of the present invention, provided that the polymers retain acceptor-type and electron mo- bility characteristics, organic small molecules, carbon nanotubes, inorganic particles (quantum dots, quantum rods, quantum tripods, ⁇ 2, ZnO etc.).
  • the photoactive layer is made of a polymer of the present invention as an electron donor and a fullerene, particularly functionalized fullerene PCBM, as an electron acceptor. These two components are mixed with a solvent and applied as a solution onto the smoothing layer by, for example, the spin-coating method, the drop casting method, the Langmuir- Blodgett ("LB") method, the ink jet printing method and the dripping method. A squeegee or printing method could also be used to coat larger surfaces with such a photoactive layer.
  • a dispersion agent such as chlorobenzene is preferably used as a solvent.
  • the vacuum deposition method, the spin-coating method, the ink jet printing method and the casting method are particularly preferred in view of ease of operation and cost.
  • the coating can be carried out using a solution and/or dispersion prepared by dissolving, or dispersing the composition in a concentration of from 0.01 to 90% by weight in an appropriate organic solvent such as benzene, toluene, xylene, tetra- hydrofurane, methyltetrahydrofurane, ⁇ , ⁇ -dimethylformamide, acetone, acetonitrile, ani- sole, dichloromethane, dimethylsulfoxide, chlorobenzene, 1 ,2-dichlorobenzene and mixtures thereof.
  • the photovoltaic (PV) device can also consist of multiple junction solar cells that are processed on top of each other in order to absorb more of the solar spectrum.
  • Such structures are, for example, described in App. Phys. Let. 90, 143512 (2007), Adv. Funct. Mater. 16, 1897-1903 (2006), WO2004/112161 and Christoph Brabec, Energy Environ. Sci 2. (2009) 347-303.
  • a so called 'tandem solar cell' comprise in this order:
  • transition layer such as an alkali halogenide, especially lithium fluoride
  • a middle electrode such as Au, Al, ZnO, T1O2 etc.
  • a transition layer such as an alkali halogenide, especially lithium fluoride
  • the PV device can also be processed on a fiber as described, for example, in
  • R 10 and R 10' are independently of each other hydrogen, halogen, cyano, Ci-C2salkyl, Ci- C25alkoxy, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C2oheteroaryl, C2- ,
  • R 22 to R 26 and R 29 to R 58 represent independently of each other H, halogen, cyano, Ci-C25alkyl, Ci-C2salkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6- C24aryl which is substituted by G, C2-C2oheteroaryl, C2-C2oheteroaryl which is substituted by G, a C4-Ci8cycloalkyl group, a C4-Ci8cycloalkyl group, which is substituted by G, C2- Ciealkenyl, C2-Ci8alkynyl, Ci-Ciealkoxy, Ci-Ciealkoxy which is substituted by E and/or interrupted by D, C7-C25aralkyl, or C 7 -C2saralkyl, which is substituted by G,
  • R 27 and R 28 are independently of each other hydrogen, Ci-C2salkyl, halogen, cyano or C 7 - C25aralkyl, or R 27 and R 28 together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the thienyl residue and which may both have up to 25 carbon atoms,
  • D is -CO-, -COO-, -S-, -0-, or -NR 112 -,
  • E is Ci-C 8 thioalkoxy, Ci-C 8 alkoxy, CN, -NR 112 R 113 , -CONR 112 R 113 , or halogen,
  • G is E, or Ci-Ciealkyl
  • R 112 and R 113 are independently of each other H; Ce-Ciearyl; Ce-Ciearyl which is substituted by Ci-Ciealkyl, or Ci-Ciealkoxy; Ci-Ciealkyl; or Ci-Ciealkyl which is interrupted by -0-, with the proviso that Ar 1 and Ar 1' are not a group of formula (XVa), if b, b', c, c', d and d' are 0 and R 10 and R 10' are independently of each other hydrogen, halogen, Ci-Cealkyl, or Ci- C 2 5alkoxy.
  • Ar 1 and Ar 1 ' are not a group of formula XVa, if b, b', c, c', d and d' are 0.
  • R 10 and R 10' are independently of each other cyano, especially a group of one of the formulae IVa to IVj.
  • R 10 and R 10' are independently of each other cyano, especially a group of one of the formulae IVa to IVj, if Ar 1 and Ar 1' are a group of formula XVa, b, b', c, c', d and d' are 0.
  • Y is a group of formula
  • U 1 is O, S, or NR 1 ;
  • U 2 is O, S, or NR 2 ;
  • T 1 and T 2 are independently of each other hydrogen, halogen, hydroxyl, cyano, -COOR 103 , - OCOR 103 , -NR 11 COR 103 , -CONR 11 R 113 , -OR 103' , -SR 103' , -SOR 103' , -S0 2 R 103' , - NR 112 S0 2 R 103' , -NR 112 R 113 , Ci-C 25 alkyl, which which may be substituted by E and/or interrupted by D, C5-Ci 2 cycloalkyl, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; C7-C 2 sarylalkyl, C6-C 2 4aryl, C6-C 24 aryl which is substituted by G, C 2 - C 2 oheteroaryl, or C 2 -C 2 oheteroaryl which is substitute
  • R 1 and R 2 may be the same or different and are selected from hydrogen, a Ci-Ciooalkyl group, -COOR 103 , -COR 103 , a Ci-Ciooalkyl group which is substituted by one or more halogen atoms, hydroxyl groups, nitro groups, -CN, or Ce-Ciearyl groups and/or interrupted by - 0-, -COO-, -OCO-, or -S-; a C7-Ciooarylalkyl group, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; a carbamoyl group, C5-Ci 2 cycloalkyl, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; a C6-C 24 aryl group, in particular phenyl or 1- or 2-naphthyl, which can be substituted one to
  • a is 1 , 2, or 3, a' is 1 , 2, or 3; wherein Ar 1 and Ar 1' are independently of each other a group of formula (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), or (XVh) (as defined in claim 1); Rio, Rio', 103, R103', Ri i2_ R113. D, E and G are as defined above.
  • Ar 1 and Ar 1 ' may be different, but are preferably the same.
  • Ar 1 and Ar 1' are independently of each other a group of formula (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), or (XVh), preferably a group of formula (XVa), (XVb), (XVc), (XVd) or (XVe), more preferably a group of formula (XVa), (XVd) or (XVe), most preferably a group of formula (XVa).
  • the compound of formula III, or an organic semiconductor material, layer or component, comprising the compound of formula III can be used in organic photovoltaics (solar cells) and photodiodes, or in an organic field effect transistor (OFET).
  • organic photovoltaics solar cells
  • OFET organic field effect transistor
  • a mixture containing the compound of formula III results in a semi-conducting layer comprising the compound of formula III (typically 5% to 99.9999% by weight, especially 20 to 85 % by weight) and at least another material.
  • the other material can be, but is not restricted to another compound of formula III, a polymer of the present invention, a semi-conducting polymer, a non-conductive polymer, organic small molecules, carbon nanotubes, a fullerene derivative, inorganic particles (quantum dots, quantum rods, quantum tripods, ⁇ 2, ZnO etc.), conductive particles (Au, Ag etc.), insulator materials like the ones described for the gate dielectric (PET, PS etc.).
  • the present invention also relates to an organic semiconductor material, layer or component, comprising a compound of formula III and to a semiconductor device, comprising a compound of formula III and/or an organic semiconductor material, layer or com- ponent.
  • the semiconductor is preferably an organic photovoltaic (PV) device (solar cell), a photodi- ode, or an organic field effect transistor.
  • PV organic photovoltaic
  • the structure and the components of the OFET device has been described in more detail above.
  • the invention provides organic photovoltaic (PV) devices (solar cells) comprising a compound of the formula III.
  • PV organic photovoltaic
  • the PV device comprise in this order:
  • transition layer such as an alkali halogenide, especially lithium fluoride
  • the photoactive layer comprises the compounds of the formula III.
  • the photoactive layer is made of a compound of the formula III, as an electron donor and an acceptor material, like a fullerene, particularly a functionalized fullerene PCBM, as an electron acceptor.
  • the photoactive layer may also contain a polymeric binder.
  • the ratio of the small molecules of formula III to the polymeric binder can vary from 5 to 95 percent.
  • the polymeric binder is a semicristalline polymer such as polystyrene (PS), high-density polyethylene (HDPE), polypropylene (PP) and polymethylmethacrylate (PMMA).
  • fullerenes useful in this invention may have a broad range of sizes (number of carbon atoms per molecule).
  • the term fullerene as used herein includes various cage-like molecules of pure carbon, including Buckminsterfullerene (C6o) and the related "spherical" fullerenes as well as carbon nanotubes.
  • Fullerenes may be selected from those known in the art ranging from, for example, C2o-Ciooo-
  • the fullerene is selected from the range of C6o to C96.
  • the fullerene is C60 or C70, such as [60]PCBM, or
  • the acceptor material can also be a material selected from the group consisting of another compounds of formula III, or any semi-conducting polymer, such as, for example, a polymer of formula I, provided that the polymers retain acceptor-type and electron mobility characteristics, organic small molecules, carbon nanotubes, inorganic particles (quantum dots, quantum rods, quantum tripods, T1O2, ZnO etc.).
  • the photoactive layer is made of a compound of the formula III, as an electron donor and a fullerene, particularly functionalized fullerene PCBM, as an electron acceptor. These two components are mixed with a solvent and applied as a solution onto the smoothing layer by, for example, the spin-coating method, the drop casting method, the Langmuir-Blodgett ("LB") method, the ink jet printing method and the dripping method. A squeegee or printing method could also be used to coat larger surfaces with such a photoactive layer.
  • a dispersion agent such as chlorobenzene is preferably used as a solvent.
  • the vacuum deposition method, the spin-coating method, the inkjet printing method and the casting method are particularly preferred in view of ease of operation and cost.
  • the coating can be carried out using a solution and/or dispersion prepared by dissolving, or dispersing the composition in a concentration of from 0.01 to 90% by weight in an appropriate organic solvent such as benzene, toluene, xylene, tetra- hydrofurane, methyltetrahydrofurane, ⁇ , ⁇ -dimethylformamide, acetone, acetonitrile, ani- sole, dichloromethane, dimethylsulfoxide, chlorobenzene, 1 ,2-dichlorobenzene and mixtures thereof.
  • the photovoltaic (PV) device can also consist of multiple junction solar cells that are processed on top of each other in order to absorb more of the solar spectrum.
  • Such structures are, for example, described in App. Phys. Let. 90, 143512 (2007), Adv. Funct. Mater. 16, 1897-1903 (2006), WO2004/112161 and Christoph Brabec, Energy Environ. Sci 2. (2009) 347-303.
  • a so called 'tandem solar cell' comprise in this order:
  • transition layer such as an alkali halogenide, especially lithium fluoride
  • a middle electrode such as Au, Al, ZnO, ⁇ 2 etc.
  • a transition layer such as an alkali halogenide, especially lithium fluoride
  • the PV device can also be processed on a fiber as described, for example, in
  • An OFET device preferably comprises:
  • the semiconductor layer comprises a compound of formula III.
  • the gate, source and drain electrodes and the insulating and semiconducting layer in the OFET device may be arranged in any sequence, provided that the source and drain elec- trade are separated from the gate electrode by the insulating layer, the gate electrode and the semiconductor layer both contact the insulating layer, and the source electrode and the drain electrode both contact the semiconducting layer.
  • the OFET comprises an insulator having a first side and a second side, a gate electrode located on the first side of the insulator, a layer comprising a compound of formula III located on the second side of the insulator, and a drain electrode and a source electrode located on the polymer layer.
  • Mobile phase 1 ,2,4-trichlorobenzene purified by vacuum distillation and stabilised by butylhydroxytoluene (BHT, 200 mg/l), Chromatographic temperature: 150°C; Mobile phase flow: 1 ml/min; Solute concentration: about 1 mg/
  • a polynomic calibration is used to calculate the molecular weight.
  • hydroquinone (1 g, 9.09 mmol) and mandelic acid (2.76 g 18.18 mmol) were dissolved in 1 ,2,4-trichlorobenzene (20 ml) and stirred for 12 h at 200 °C. After cooling to 60 °C, nitrobenzene (2.3 ml) was added and the mixture was stirred for another hour at 200 °C. After cooling to room temperature, 50 ml methanol were added. A precipitate formed, which was filtered off, washed with methanol and dried in air. 3a was obtained as a yellow solid (2.32 g, 75 %).
  • Polymer 21 was made from compound 16 according to the procedure for polymer 20.
  • 9,9-di-n- hexylfluorene-2,7'-bispinakolato-boronester was synthesized according to the literature: Jo, J.; Chi, C; Hoger, S.; Wegner, G.; Yoon, D. Y. Chem. Eur. J. 2004, 10, 2681.
  • the synthesis of polymer 5 was made from 1 equ. of compound 3f and 1 equ. of 9,9-di-n- hexylfluorene-2,7'-bispinakolato-boronester via Suzuki polymerization according to known methods with Pd(PPh 3 ) 4 as catalyst and K2CO3 as base in water-toluene mixture.
  • the 1 H NMR spectra of polymer 5 is shown in Fig. 1.
  • 2,5-Bis(trimethylstannyl)thiophene was synthesized according to the literature: C. Van Pham, R.S. Macomber, H.B. Mark Jr, H. Zimmer, J. Org. C ?em.1984, 49, 5250.
  • polymer 6 was made from 1 equ. of compound 3f and 1 equ. of 2,5- Bis(trimethylstannyl)thiophene via Stille polymerization according to known methods with Pd(PPh 3 ) 4 as catalyst in toluene.
  • the 1 H NMR spectra of polymer 6 is shown in Fig. 2. 3,4-ethylenedioxythien-2-yl trimethylstannane and 3,4-ethylenedithiathien-2-yl trimethyl- stannane where synthesized according to the litterature: C.Wang, J.L. Schindler, C.R. Kan- newurf, M.G. Kanatzidis, Chem. Mater. 1995, 7, 58.
  • the four monomers 7a, 7b, 9a and 9b were homo-electropolymerized by repetitive cycling over the redox active range of the materials.
  • Scan rate: 100 mV s 1 ; T 20 °C.
  • the cyclovoltammetric response of the four polymers was studied using films of the polymers on a glassy carbon working electrode in acetonitrile vs. Ag/AgCI.

Abstract

The present invention relates to polymers comprising one or more (repeating) unit(s) of the formula (I): wherein Y is a group of formula (AA), or (BB) and their use as organic semiconductor in organic devices, especially in organic photovoltaics (solar cells) and photodiodes, or in a device containing a diode and/or an organic field effect transistor. The polymers according to the invention 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.

Description

Polymers based on Benzodiones
Description The present invention relates to polymers comprising one or more (repeating) unit(s) of the formula I, and their use as organic semiconductor in organic devices, especially in organic photovoltaics (solar cells) and photodiodes, or in a device containing a diode and/or an organic field effect transistor. The polymers according to the invention 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.
C. W. Greenhalgh et al., Journal of Dyers and Colourists 110 (1994) 178-183 describes the synthesis and properties of certain benzodifurane compounds as well as their application to disperse dyes:
Figure imgf000002_0001
Figure imgf000003_0001
T1 and T2 are a group Experimental details can be found in C. W. Greenhalgh et al., Dyes and Pigments 1 (1980) 103.
K. Nakano et al., Synthetic Metals 159 (2009) 939-942 reports the synthesis of π- conjugated copolymer with dibenzo[d,d']benzo[1 ,2-b:4,5-b']difurane (DBBF) unit in the main chain. Copolymerisation of 6,12-diiodo DBBF with p-diethynylbenzene- or 2,7- diethynylfluorene under Sonogashira-Hagiwara coupling reaction conditions gave the corresponding copolymers.
EP1344788A1 relates to polymer compounds comprising dibenzofurane, or dibenzo thio- phene repeating units
EP0436940A1 discloses a process for the production of benzodifurane compounds of for-
mula
Figure imgf000003_0002
wherein R and R' are independently of each other a naphthyl group, or an unsubstituted or substituted phenyl group.
It is the object of the present invention to provide polymers, which show high efficiency of energy conversion, excellent field-effect mobility, good on/off current ratios and/or excellent stability, when used in organic field effect transistors, organic photovoltaics (solar cells) and photodiodes. Said object has been solved by polymers comprising one or more (repeating) unit(s) of the
formula
Figure imgf000004_0001
, or (Y), especially polymers comprising one or more (repeating) unit(s) of the formula
Figure imgf000004_0002
wherein Y is a group of formula
a is 1 , 2, or 3, a' is 1 , 2, or 3; b is
Figure imgf000004_0003
c' is 0, 1 , 2, or 3; d is 0, 1 , 2, or 3; d' is 0, 1 , 2, or 3;
U1 is O, S, or NR1 ;
U2 is O, S, or NR2;
T1 and T2 are independently of each other hydrogen, halogen, hydroxyl, cyano, -COOR103, - OCOR103, -NR11 COR103, -CONR11 R113, -OR103', -SR103', -SOR103', -S02R103', - NR112S02R103', -NR112R113, Ci-C25alkyl, which may be substituted by E and/or interrupted by D, C5-Ci2cycloalkyl, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; C7-C2sarylalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2- C2oheteroaryl, or C2-C2oheteroaryl which is substituted by G;
R1 and R2 may be the same or different and are selected from hydrogen, a Ci-Ciooalkyl group, -COOR103, -COR103, a Ci-Ciooalkyl group which is substituted by one or more halogen atoms, hydroxyl groups, nitro groups, -CN, or C6-Ci8aryl groups and/or interrupted by - 0-, -COO-, -OCO-, or -S-; a C7-Ciooarylalkyl group, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; a carbamoyl group, C5-Ci2cycloalkyl, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; a C6-C24aryl group, in particular phenyl or 1- or 2-naphthyl, which can be substituted one to three times with Ci- Cealkyl, Ci-Cethioalkoxy, and/or Ci-Cealkoxy, or pentafluorophenyl,
R103 and R103' are independently of each other Ci-Ciooalkyl, especially C3-C2salkyl, Ci- C25alkyl substituted by E and/or interrupted by D, C7-C2sarylalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C2oheteroaryl, or C2-C2oheteroaryl which is substituted by G, Ar2, Ar2', Ar3, Ar3', Ar4 and Ar4' have the meaning of Ar1 , or are independently of each other
Figure imgf000004_0004
Figure imgf000005_0001
Figure imgf000006_0001
R3 and R3' are independently of each other hydrogen, halogen, halogenated Ci-C2salkyl, especially CF3, cyano, Ci-C2salkyl, especially C3-C25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C7-C2sarylalkyl, or Ci-C2salkoxy;
R104 and R104' are independently of each other hydrogen, cyano, COOR103, or a Ci-C2salkyl group,
R4, R4', R5, R5', R6 and R6' are independently of each other hydrogen, halogen, halogenated Ci-C25alkyl, especially CF3, cyano, Ci-C2salkyl, especially C3-C2salkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C7-C2sarylalkyl, or Ci-C2salkoxy; R114 is Ci-C25alkyl, especially C3-C2salkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms,
R7, R7', R9 and R9' are independently of each other hydrogen, Ci-C2salkyl, especially C3- C25alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms; or C7-C25arylalkyl,
R8 and R8' are independently of each other hydrogen, C6-Ci8aryl; C6-Ci8aryl which is substituted by Ci-Ciealkyl, or Ci-Ciealkoxy; or Ci-C2salkyl, especially C3-C2salkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C7-C2sarylalkyl, R11 and R11 ' are independently of each other Ci-C2salkyl group, especially a Ci-Cealkyl group, C7-C25arylalkyl, or a phenyl group, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy;
R12 and R12' are independently of each other hydrogen, halogen, cyano, Ci-C2salkyl, especially C3-C25alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, Ci-C25alkoxy, C7-C25arylalkyl, or ^ , wherein R13 is a Ci-Cioalkyl group, or a tri(Ci-C8alkyl)silyl group;
Figure imgf000007_0001
R105, R105', R106 and R106'are independently of each other hydrogen, halogen, cyano, Ci- C25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C7-C25arylalkyl, or Ci-Ciealkoxy,
R107 is hydrogen, C7-C2sarylalkyl, C6-Ci8aryl; C6-Ci8aryl which is substituted by Ci-Ciealkyl, or Ci-Ciealkoxy; Ci-Ci8perfluoroalkyl; Ci-C2salkyl; especially C3-C2salkyl, which may be interrupted by -0-, or -S-; or -COOR103; R103 is is as defined above;
R108 and R109 are independently of each other H, Ci-C2salkyl, Ci-C2salkyl which is substituted by E and/or interrupted by D, C7-C2sarylalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C2oheteroaryl, C2-C2oheteroaryl which is substituted by G, C2-Ci8alkenyl, C2- Ciealkynyl, Ci-Ciealkoxy, Ci-Ciealkoxy which is substituted by E and/or interrupted by D, or C7-C25aralkyl, or
R108 and R109 together form a group of formula =CR110R111 , wherein
R110 and R111 are independently of each other H, Ci-Ciealkyl, Ci-Ciealkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6-C24aryl which is substituted by G, or C2- C2oheteroaryl, or C2-C2oheteroaryl which is substituted by G, or
R108 and R109 together form a five or six membered ring, which optionally can be substituted by Ci-Ciealkyl, Ci-Ciealkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6- C24aryl which is substituted by G, C2-C2oheteroaryl, C2-C2oheteroaryl which is substituted by G, C2-Ci8alkenyl, C2-Ci8alkynyl, Ci-Ciealkoxy, Ci-Ciealkoxy which is substituted by E and/or interrupted by D, or C7-C2saralkyl,
D is -CO-, -COO-, -S-, -0-, or -N R112-,
E is Ci-C8thioalkoxy, Ci-C8alkoxy, CN, -NR^Rm, -CONR112R113, or halogen,
G is E, or Ci-Ciealkyl, and
R112 and R113 are independently of each other H; C6-Ci8aryl; C6-Ci8aryl which is substituted by Ci-Ciealkyl, or Ci-Ciealkoxy; Ci-Ciealkyl; or Ci-Ciealkyl which is interrupted by -0-. Advantageously, the polymer of the present invention, or an organic semiconductor material, layer or component, comprising the polymer of the present invention can be used in organic photovoltaics (solar cells) and photodiodes, or in an organic field effect transistor (OFET).
The term polymer comprises oligomers as well as polymers. The oligomers of this invention have a weight average molecular weight of < 4,000 Daltons. The polymers of this invention preferably have a weight average molecular weight of 4,000 Daltons or greater, especially
4.000 to 2,000,000 Daltons, more preferably 10,000 to 1 ,000,000 and most preferably 10,000 to 100,000 Daltons. Molecular weights are determined according to high- temperature gel permeation chromatography (HT-GPC) using polystyrene standards. The polymers of this invention preferably have a polydispersity of 1.01 to 10, more preferably
1.1 to 3.0, most preferred 1.5 to 2.5. The polymers of the present invention are preferably conjugated.
In an embodiment of the present invention the polymer is a polymer of formula
Figure imgf000008_0001
wherein n is usually in the range of 4 to 1000, especially 4 to 200, very especially 5 to 150. U1 is preferably O or NR1 ; more preferably NR1.
U2 is preferably O or NR1 ; more preferably NR1.
Preferably, T1 and T2 are independently of each other hydrogen, halogen, cyano, - COOR103, -OCOR103, -OR103, -SR103, or Ci-C25alkyl, which may be substituted by E and/or interrupted by D; more preferably hydrogen, halogen, cyano, -OR103, Ci-C2salkyl. Most preferred T1 and T2 are hydrogen, or Ci-C2salkyl, especially hydrogen.
R1 and R2 may be different, but are preferably the same; and are preferably selected from hydrogen, a Ci-Ciooalkyl group, a Ci-Ciooalkyl group which is substituted by one or more halogen atoms, -CN, or C6-Ci8aryl groups and/or interrupted by -0-, -COO-, -OCO-, or -S-; a C7-C24arylalkyl group, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; and pentafluorophenyl. More preferably R1 and R2 are selected from hydrogen, a Ci-C38alkyl group, a Ci-C38alkyl group which is substituted by one or more halogen atoms; a C7-C2sarylalkyl group, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; and pentafluorophenyl. Still more preferably R1 and R2 are selected from hydrogen and a Ci-C38alkyl group. Most preferred R1 and R2 are a Ci-C38alkyl group such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, 1 ,1 ,3,3-tetramethylpentyl, n- hexyl, 1 -methyl hexyl, 1 ,1 ,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3- tetramethyl butyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2- ethylhexyl, n-nonyl, decyl, undecyl, especially n-dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, 2-ethyl-hexyl, 2-butyl-hexyl, 2-butyl-octyl, 2-hexyldecyl, 2-decyl-tetradecyl, hep- tadecyl, octadecyl, eicosyl, heneicosyl, docosyl, or tetracosyl.
Figure imgf000009_0001
Advantageously, the groups R1 and R2 can be represented by formula
wherein ml = n 1 + 2 and ml + n1 < 24. Chiral side chains, such as R1 and R2, can either be enantiomerically pure, homochiral, or racemic, which can influence the morphology of the polymers.
Preferably, R103 and R103' are independently of each other Ci-C2salkyl, Ci-C2salkyl substituted by halogen, especially CF3, C7-C2sarylalkyl, or phenyl; more preferably Ci-C2salkyl.
Figure imgf000009_0002
Preferably, Ar2, Ar2', Ar3, Ar3', Ar4 and Ar4' are independently of each other a group of formula (Xa), (Xb), (Xc), (Xd), (Xe), (Xg), (Xh), (Xk), (XI), (Xm), (Xn), (Xo), (Xp), (Xv), (Xx), (Xy), (Xz), (XIa), (Xlb), (Xlc), (Xld), (Xle), (Xlf), (Xlg), (Xlh), (Xli), (XII), or (Xlm); more preferably a group of formula (Xa), (Xc), (Xg), (Xh), (Xm), (Xn), (Xo), (Xp), (Xy), (Xle), (Xlf), (XII), or (Xlm), still more preferably a group of formula (Xa), (Xm), (Xn), (Xo), or (Xlm), most preferred a group of formula (Xa), (Xm), or (Xn), especially (Xm). Preferably, R3 and R3' are independently of each other hydrogen, halogen, CF3, cyano, Ci- C25alkyl or Ci-C2salkoxy; more preferably CF3, cyano or Ci-C2salkyl; most preferred hydrogen, or Ci-C25alkyl. Preferably, R104 and R104' are independently of each other hydrogen, cyano or a Ci-C2salkyl group, more preferably hydrogen, or a Ci-C2salkyl group, most preferred hydrogen.
Preferably, R4, R4', R5, R5', R6 and R6' are independently of each other hydrogen, halogen, CF3, cyano, Ci-C2salkyl or Ci-C2salkoxy, more preferably hydrogen, CF3, cyano or Ci- C25alkyl; most preferred hydrogen, or Ci-C2salkyl.
Preferably R7, R7', R9 and R9' are independently of each other hydrogen, Ci-C2salkyl, more preferably C4-C2salkyl. Preferably, R8 and R8' are independently of each other hydrogen, Ci-C2salkyl, Ci-C2salkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or
C7-C25arylalkyl, more preferably hydrogen, or Ci-C2salkyl.,
Preferably, R11 and R11 ' are independently of each other a Ci-C2salkyl group, especially a Ci-Cealkyl group, or phenyl; more preferably a Ci-Cealkyl group.
Preferably, R12 and R12' are independently of each other hydrogen, Ci-C2salkyl, Ci-
C25alkoxy, or ^ , wherein R13 is a Ci-Cioalkyl group, or a tri(Ci-C8alkyl)silyl group, more preferably hydrogen, Ci-C2salkyl, or Ci-C2salkoxy.
If Ar2, Ar2', Ar3, Ar3', Ar4 and Ar4' have the meaning of Ar1, they are independently of each other a group of formula (XVa), (XVb), (XVc), (XVd) or (XVe), preferably a group of formula (XVa), (XVd) or (XVe), more preferably a group of formula (XVa). Preferably, R105, R105', R106 and R106'are independently of each other hydrogen, halogen, cyano, Ci-C2salkyl or Ci-Ciealkoxy, more preferably Ci-C2salkyl or Ci-Ciealkoxy, most pref- ered hydrogen, or Ci-C2salkyl.
R107 is preferably hydrogen, Ci-C2salkyl, Ci-C2salkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C7-C2sarylalkyl, more preferably hydrogen, or Ci- C25alkyl, most preferred C4-C2salkyl.
Preferably, R108 and R109 are independently of each other H, Ci-C2salkyl, Ci-C2salkyl which is substituted by E and/or interrupted by D, C7-C2sarylalkyl, C2-Ci8alkenyl, or C7-C2saralkyl, or R108 and R109 together form a five or six membered ring, which optionally can be substituted by Ci-Ciealkyl, Ci-Ciealkyl which is substituted by E and/or interrupted by D, C6- C24aryl, C6-C24aryl which is substituted by G, D is -CO-, -COO-, -S- or -0-, E is Ci- Cethioalkoxy, Ci-Cealkoxy, CN or halogen, G is E, or Ci-Ciealkyl. More preferably, R108 and R109 are independently of each other H, Ci-C2salkyl or C7-C2sarylalkyl. Most preferred R108 and R109 are independently of each other H, or Ci-C2salkyl. D is preferably -CO-, -COO-, -S- or -0-, more preferably -COO-, -S- or -0-, most preferred - S- or -0-. Preferably, E is Ci-Cethioalkoxy, Ci-Cealkoxy, CN, or halogen, more preferably Ci- Cealkoxy, CN, or halogen, most preferred halogen, especially F.
Preferably, R112 and R113 are independently of each other H; Ci-Ciealkyl; or Ci-Ciealkyl which is interrupted by -O-, more preferably H, or Ci-Ciealkyl; most preferred Ci-Ciealkyl.
In a preferred embodiment the present invention is directed to polymers comprising one or more (repeating) unit(s) of the formula
Figure imgf000011_0001
U1 is O, S, or NR1;
U2 is O, S, or NR2;
T1 and T2 are independently of each other hydrogen, halogen, hydroxyl, cyano, -COOR103, - OCOR103, -NR11 COR103, -CONR11 R113, -OR103', -SR103', -SOR103', -S02R103', - NR112S02R103', -NR112R113, Ci-C25alkyl, which which may be substituted by E and/or inter- rupted by D, C5-Ci2cycloalkyl, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; C7-C2sarylalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2- C2oheteroaryl, or C2-C2oheteroaryl which is substituted by G;
R1 and R2 may be the same or different and are selected from hydrogen, a Ci-Ciooalkyl group, -COOR103, -COR103, a Ci-Ciooalkyl group which is substituted by one or more halo- gen atoms, hydroxyl groups, nitro groups, -CN, or C6-Ci8aryl groups and/or interrupted by - 0-, -COO-, -OCO-, or -S-; a C7-Ciooarylalkyl group, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; a carbamoyl group, C5-Ci2cycloalkyl, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; a C6-C24aryl group, in particular phenyl or 1- or 2-naphthyl, which can be substituted one to three times with Ci- Cealkyl, Ci-Cethioalkoxy, and/or Ci-Cealkoxy, or pentafluorophenyl;
a is 1 , 2, or 3, a' is 1 , 2, or 3; wherein Ar1 and Ar1' are independently of each other a group of formula (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg) or (XVh) (as defined in claim 1); and R103, R103', R112, R113, D, E and G are as defined above; or a polymer comprising one or more (repeating) unit(s) of the formula
Figure imgf000012_0001
(I"), wherein a is 1 , or 2; a' is 1 , or 2; b is 1 , 2, or 3; b' is 1 , 2, or 3; wherein Y, Ar1 and Ar1 ' are as defined above; and Ar2 and Ar2' are as defined above.
In said embodiment Y is preferably a group of formula
Figure imgf000012_0002
. U1 and U2 may be different, but are preferably the same. U1 is preferably O or NR1 ; more preferably NR1. U2 is preferably O or NR1 ; more preferably NR1.
T1 and T2 may be different, but are preferably the same. T1 and T2 are preferably independently of each other hydrogen, halogen, cyano, -COOR103, -OCOR103, -OR103, -SR103, Ci-C25alkyl, which may be substituted by E and/or interrupted by D; more preferably hydrogen, halogen, cyano, -OR103, Ci-C2salkyl; most preferred hydrogen, or Ci-C2salkyl, especially hydrogen. R1 and R2 may be different, but are preferably the same. Preferably, R1 and R2 are selected from hydrogen, a Ci-Ciooalkyl group, a Ci-Ciooalkyl group which is substituted by one or more halogen atoms, -CN, or C6-Ci8aryl groups and/or interrupted by -O-, -COO-, -OCO-, or -S-; a C7-Ciooarylalkyl group, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; and pentafluorophenyl. More preferably R1 and R2 are selected from hydrogen, a Ci-C38alkyl group, a Ci-C38alkyl group which is substituted by one or more halogen atoms; a C7-C24arylalkyl group, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; and pentafluorophenyl; most preferred R1 and R2 are selected from hydrogen, or a Ci-C38alkyl group; especially a Ci-C38alkyl group. a and a' may be different, but are preferably the same, a and a' are preferably 1 , or 2, more preferably 1.
Ar2 and Ar2' may be different, but are preferably the same. Preferably, Ar2 and Ar2' are independently of each a group of formula (Xa), (Xb), (Xc), (Xd), (Xe), (Xg), (Xh), (Xk), (XI), (Xm), (Xn), (Xo), (Xp), (Xv), (Xx), (Xy), (Xz), (Xla), (Xlb), (Xlc), (Xld), (Xle), (Xlf), (Xlg), (Xlh), (Xli), (XII), or (Xlm) (as defined above).
More preferably, Ar2 and Ar2' are a group of formula (Xa), (Xc), (Xg), (Xh), (Xm), (Xn), (Xo), (Xp), (Xy), (Xle), (Xlf) and (Xlm). Still more preferably Ar2 and Ar2' are a group of formula (Xa), (Xm), (Xn), (Xo) and (Xlm). Most preferred Ar2 and Ar2' are a group of formula (Xa), (Xm) and (Xn), especially (Xm). Ar1 and Ar1 ' may be different, but are preferably the same. Ar1 and Ar1' are independently of each other a group of formula (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), or (XVh), preferably a group of formula (XVa), (XVb), (XVc), (XVd) or (XVe), more preferably a group of formula (XVa), (XVd) or (XVe), most preferably a group of formula (XVa).
In a further preferred embodiment the present invention is directed to polymers, comprising one or more (repeating) unit(s) of the formula
Figure imgf000013_0001
Figure imgf000014_0001
U1 is O, or NR1 ;
U2 is O, or NR2;
T1 and T2 are independently of each other hydrogen, or Ci-C2salkyl, especially hydrogen; R1 and R2 may be the same or different and are selected from a Ci-C38alkyl group, especially Ce-C36alkyl group;
RIO5I 105', R106 anc| Rio6 are independently of each other hydrogen or Ci-C2salkyl; and R107 and R107' are independently of each other hydrogen or Ci-C2salkyl, especially Ci- C25alkyl;
R108 and R1°9 are independently of each other H, or Ci-C25alkyl [Okay?].
Repeating) unit(s) of the formula (la); (lb); (Id); (le); (If) or (Ih) are preferred; repeating unit(s) of the formula (la); (Id); (le) or (Ih) are more preferred; repeating unit(s) of the formula (la), or (le) are most preferred.
Preferably U1 and U2 are the same.
Preferably T1 and T2 are the same.
In another embodiment the present invention is directed to polymers, comprising (repeat- ing) unit(s) of the formula
Figure imgf000014_0002
(II), wherein
A is a repeating unit of formula (I), and -COM1- is a repeating unit, which has the meaning of Ar2, wherein Ar2 are as defined
14 15 17
-Ar -Ar -Ar- -Ar
above, or a group of formula
k is 1 , 1 is 1 , r is 0, or 1 , z is 0, or 1 , and
Ar14, Ar15, Ar16 and Ar17 are independently of each other a group of formula
Figure imgf000015_0001
wherein one of X5 and X6 is N and the other is CR14, and
R14, R14', R17 and R17' are independently of each other H, or a Ci-C2salkyl group, especially a C6-C25alkyl, which may optionally be interrupted by one or more oxygen atoms. Examples of repeating units -COM1- are groups of formula (Xa) to (Xz), (Xla) to (Xln) and (XVa) to (XVh). Among these groups groups of formula (Xa), (Xb), (Xc), (Xg), (XI), (Xm), (Xn), (Xo), (Xle), (Xlf), (XII), (Xlm), (Xln), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf) and (XVg) are preferred, groups of formula (Xa), (Xg), (XI), (Xm), (Xle), (Xlf), (Xlm), (XVa), (XVb), (XVd), and (XVe), are more preferred, groups of formula (Xa), (XI), (Xm), (Xle), (Xlm), (XVa), (XVb), and (XVd) are still more preferred. Groups formula (Xa), (Xm) and (Xlm) are most preferred.
14 15 17
-Ar -Ar -Ar- -Ar
are
Figure imgf000015_0002
or Ci-C25alky, R104 and R104' preferably are independently of each other hydrogen, cyano or a Ci-C25alkyl group, and R14 and R14 are independently of each other H, or a Ci-C2salkyl group, especially a C6-C2salkyl, which may optionally be interrupted by one or more oxygen atoms. In a preferred embodiment of the present invention the polymer is a copolymer, comprising
-COM1
repeating units of formula (VII), especially a copolymer of for-
1
-COM1
n
mula , wherein A and COM1 are as defined above; n is number which results in a molecular weight of 4,000 to 2,000,000 Daltons, more preferably 10,000 to 1 ,000,000 and most preferably 10,000 to 100,000 Daltons. n is usually in the range of 4 to 1000, especially 4 to 200, very especially 5 to 150.
In a preferred embodiment the present invention is directed to polymers, wherein A is a
-COM .11 repeating unit of formula (la), (Id), (le), or (Ih) (as defined in claim 3) and
is
Figure imgf000016_0001
or , where R3 and R3' are independently of each other hydrogen, or Ci-C25alky, R104 and R104' are independently of each other hydrogen, cyano or a Ci- C25alkyl group, and R14 and R14 are independently of each other H, or a Ci-C2salkyl group, especially a C6-C2salkyl, which may optionally be interrupted by one or more oxygen atoms.
Preferred polymers are shown below:
Figure imgf000016_0002
Figure imgf000017_0001
n is 4 to 1000, especially 4 to 200, very especially 5 to 100,
T1 and T2 are independently of each other hydrogen, or Ci-C2salkyl, especially hydrogen; R1 is a Ci-C38alkyl group, especially a Ce-C36alkyl group,
R3 is hydrogen, halogen, cyano, Ci-C2salkyl or Ci-C2salkoxy, especially hydrogen or Ci- C25alkyl;
R105 and R105' are independently of each other hydrogen, halogen, cyano, Ci-C2salkyl or Ci- C25alkoxy, especially hydrogen or Ci-C2salkyl;
R106 and R106' are independently of each other hydrogen or Ci-C2salkyl; and
R108 and R109 are independently of each other H, or Ci-C2salkyl.
Examples of preferred polymers are shown below:
P C.H,.. ΟΉ
Figure imgf000017_0002
Figure imgf000018_0001
n is usually in the range of 4 to 1000, especially 4 to 200, very especially 5 to 150.
The polymers of the present invention can comprise more than 2 different repeating units, such as, for example, repeating units A, B and D, which are different from each other. If the polymers comprise repeating units of the formul , they
Figure imgf000018_0002
are preferably (random) copolymers of formula , wherein x =
0.995 to 0.005, y = 0.005 to 0.995, especially x = 0.2 to 0.8, y = 0.8 to 0.2, and wherein x + y = 1. A is a repeating unit of formula (I), D* is a repeating unit -COM1- and B is a repeating unit -COM1-, or a repeating unit of formula (I); with the proviso that A, B and D* are different from each other.
Copolymers of formula VII can be obtained, for example, by the Suzuki reaction. The condensation reaction of an aromatic boronate and a halogenide, especially a bromide, commonly referred to as the "Suzuki reaction", is tolerant of the presence of a variety of organic functional groups as reported by N. Miyaura and A. Suzuki in Chemical Reviews, Vol. 95, pp. 457-2483 (1995). Preferred catalysts are 2-dicyclohexylphosphino-2',6'-di- alkoxybiphenyl/palladium(ll)acetates, tri-alykl-phosphonium salts/palladium (0) derivatives and tri-alkylphosphine/palladium (0) derivatives. Especially preferred catalysts are 2- dicyclohexylphosphino-2',6'-di-methoxybiphenyl (sPhos)/palladium(ll)acetate and, tri-tert- butylphosphonium tetrafluoroborate ((t-Bu)3P * HBF4)/tris(dibenzylideneacetone) dipalla- dium (0) (Pd2(dba)3) and tri-tert-butylphosphine (t-Bu)3P/tris(dibenzylideneacetone) dipalla- dium (0) (Pd2(dba)3). This reaction can be applied to preparing high molecular weight polymers and copolymers.
To prepare polymers corresponding to formula VII a dihalogenide of formula
is reacted with an (equimolar) amount of a diboronic acid or diboronate corresponding to
-COM1- -X' X -COML X formula ; or a dihalogenide of formula is reacted with an (equimolar) amount of a diboronic acid or diboronate corresponding to formula
Λ , wherein X10 is halogen, especially Br, and X11 is independently in each oc-
currence -B(OH)2, -B(OY1)2,
Figure imgf000019_0001
, wherein Y1 is independently in each occurrence a Ci-Cioalkyl group and Y2 is independently in each occurrence a C2-Ci0alkylene group, such as -CY3Y4-CYSY6-, or -θΥ ^-ΟΥδΥ - CY11Y12-, wherein Y3, Y4, Y5, Y6, Y , ye, Y9, γιο, γι ι anc| γΐ2 are independently of each other hydrogen, or a Ci- Cioalkyl group, especially -C(CH3)2C(CH3)2-, -CH2C(CH3)2CH2-, or -C(CH3)2CH2C(CH3)2-, and Y13 and Y14 are independently of each other hydrogen, or a Ci-Cioalkyl group, under the catalytic action of Pd and triphenylphosphine. The reaction is typically conducted at about 0 °C to 180 °C in an aromatic hydrocarbon solvent such as toluene, xylene. Other solvents such as dimethylformamide, dioxane, dimethoxyethan and tetrahydrofuran can also be used alone, or in mixtures with an aromatic hydrocarbon. An aqueous base, preferably sodium carbonate or bicarbonate, potassium phosphate, potassium carbonate or bicarbonate is used as activation agent for the boronic acid, boronate and as the HBr scav- enger. A polymerization reaction may take 0.2 to 100 hours. Organic bases, such as, for example, tetraalkylammonium hydroxide, and phase transfer catalysts, such as, for example TBAB, can promote the activity of the boron (see, for example, Leadbeater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 and references cited therein). Other variations of reaction conditions are given by T. I. Wallow and B. M. Novak in J. Org. Chem. 59 (1994) 5034-5037; and M. Remmers, M. Schulze, and G. Wegner in Macromol. Rapid Commun. 17 (1996) 239-252. Controll of molecular weight is possible by using either an excess of dibromide, diboronic acid, or diboronate, or a chain terminator.
According to the process described in WO2010/136352 (PCT/EP2010/056776) the polym- erisation is carried out in presence of
a) a catalyst/ligand system comprising a palladium catalyst and an organic phosphine or phosphonium compound,
b) a base,
c) a solvent or a mixture of solvents, characterized in that
the organic phosphine is a trisubstituted phosphine of formula
Figure imgf000020_0001
(VI), or phosphonium salt thereof, wherein X" independently of Y" represents a nitrogen atom or a C-R2" group and Y" independently of X" represents a nitrogen atom or a C-R9" group, R1" for each of the two R1" groups independently of the other represents a radical selected from the group Ci-C24-alkyl, C3-C2o-cycloalkyl, which includes especially both monocyclic and also bi-and tri-cyclic cycloalkyi radicals, Cs-Cw-aryl, which includes especially the phenyl, naphthyl, fluorenyl radical, C2-Ci3-heteroaryl, wherein the number of hetero atoms, selected from the group N, O, S, may be from 1 to 2, wherein the two radicals R1" may also be linked to one another,
and wherein the above-mentioned radicals R1" may themselves each be mono-or poly- substituted independently of one another by substituents selected from the group hydrogen, Ci-C2o-alkyl, C2-C20-alkenyl, C3-C8-cycloalkyl, C2-Cg-hetero-alkyl, Cs-Cio-aryl, C2-C9- heteroaryl, wherein the number of hetero atoms from the group N, O, S may be from 1 to 4, Ci-C2o-alkoxy, Ci-Cio-haloalkyl, hydroxy, amino of the forms NH-(Ci-C2o-alkyl), NH-(C5-Cio- aryl), N(Ci-C2o-alkyl)2, N(Ci-C20-alkyl) (C5-Ci0-aryl), N(C5-Ci0-aryl)2, N(Ci-C2o-alkyl/C5-Ci0- aryl3)3+, NH-CO-Ci-C20-alkyl, NH-CO- C5-Ci0-aryl, carboxylato of the forms COOH and COOQ (wherein Q represents either a monovalent cation or Ci-Ce-alkyl), G-C6-acyloxy, sulfinato, sulfonato of the forms SO3H and SO3Q' (wherein Q' represents either a monovalent cation, Ci-C2o-alkyl, or Cs-Cio-aryl), tri-Ci -Ce-al kylsi lyl , wherein two of the mentioned substituents may also be bridged with one another, R2"-R9" represent a hydrogen, alkyl, alkenyl, cycloalkyi, aromatic or heteroaromatic aryl, O-alkyl, NH- alkyl, N-(alkyl)2, O-(aryl), NH-(aryl), N-(alkyl)(aryl), O-CO-alkyl, O-CO-aryl, F, Si(alkyl)3, CF3, CN, C02H, COH, SO3H, CON H2, CONH(alkyl), CON(alkyl)2, S02(alkyl), SO(alkyl), SO(aryl), S02(aryl), S03(alkyl), S03(aryl), S-alkyl, S-aryl, NH-CO(alkyl), C02(alkyl), CONH2, CO(alkyl), NHCOH, N HC02(alkyl), CO(aryl), C02(aryl) radical, wherein two or more adjacent radicals, each independently of the other (s), may also be linked to one another so that a condensed ring system is present and wherein in R2" to R9" alkyl represents a hydrocarbon radical having from 1 to 20 carbon atoms which may in each case be linear or branched, alkenyl represents a mono-or poly- unsaturated hydrocarbon radical having from 2 to 20 carbon atoms which may in each case be linear or branched, cycloalkyi represents a hydrocarbon having from 3 to 20 carbon atoms, aryl represents a 5- to 14-membered aromatic radical, wherein from one to four carbon atoms in the aryl radical may also be replaced by hetero atoms from the group nitrogen, oxygen and sulfur so that a 5- to 14-membered heteroaromatic radical is present, wherein the radicals R2" to R9" may also carry further substituents as defined for R1".
The organic phosphines and their synthesis are described in WO2004101581.
Preferred organic phosphines are selected from trisubstituted phosphines of formula
Figure imgf000021_0001
1 R5" and R6" together form a ring 2) R3" and R4" together form a ring
Examples of preferred catalysts include the following compounds:
palladium(ll) acetylacetonate, palladium(O) dibenzylidene-acetone complexes, palladium(ll) propionate,
Pd2(dba)3: [tris(dibenzylideneacetone) dipalladium(O)],
Pd(dba)2: [bis(dibenzylideneacetone) palladium(O)],
Pd(PR3)2, wherein PR3 is a trisubstituted phosphine of formula VI,
Pd(OAc)2: [palladium(ll) acetate], palladium(ll) chloride, palladium(ll) bromide, lithium tetra- chloropalladate(ll),
PdCl2(PR3)2; wherein PR3 is a trisubstituted phosphine of formula VI; palladium(O) diallyl ether complexes, palladium(ll) nitrate,
PdCI2(PhCN)2: [dichlorobis(benzonitrile) palladium(ll)],
PdCI2(CH3CN): [dichlorobis(acetonitrile) palladium(ll)], and
PdCI2(COD): [dichloro(1 ,5-cyclooctadiene) palladium(ll)].
Especially preferred are PdCI2, Pd2(dba)3, Pd(dba)2, Pd(OAc)2, or Pd(PR3)2. Most preferred are Pd2(dba)3 and Pd(OAc)2. The palladium catalyst is present in the reaction mixture in catalytic amounts. The term "catalytic amount" refers to an amount that is clearly below one equivalent of the (het- ero)aromatic compound(s), preferably 0.001 to 5 mol-%, most preferably 0.001 to 1 mol-%, based on the equivalents of the (hetero)aromatic compound(s) used.
The amount of phosphines or phosphonium salts in the reaction mixture is preferably from 0.001 to 10 mol-%, most preferably 0.01 to 5 mol-%, based on the equivalents of the (het- ero)aromatic compound(s) used. The preferred ratio of Pd:phosphine is 1 :4. The base can be selected from all aqueous and nonaqueous bases and can be inorganic, or organic. It is preferable that at least 1.5 equivalents of said base per functional boron group is present in the reaction mixture. Suitable bases are, for example, alkali and alkaline earth metal hydroxides, carboxylates, carbonates, fluorides and phosphates such as sodium and potassium hydroxide, acetate, carbonate, fluoride and phosphate or also metal alcoholates. It is also possible to use a mixture of bases. The base is preferably a lithium salt, such as, for example, lithium alkoxides (such as, for example, lithium methoxide and lithium ethoxide), lithium hydroxide, carboxylate, carbonate, fluoride and/or phosphate.
The at present most preferred base is aqueous LiOHxh O (monohydrate of LiOH) and (wa- terfree) LiOH.
The reaction is typically conducted at about 0 °C to 180 °C, preferably from 20 to 160°C, more preferably from 40 to 140°C and most preferably from 40 to 120°C. A polymerization reaction may take 0.1 , especially 0.2 to 100 hours.
In a preferred embodiment of the present invention the solvent is THF, the base is
LiOH*H20 and the reaction is conducted at reflux temperature of THF (about 65 °C).
The solvent is for example selected from toluene, xylenes, anisole, THF, 2- methyltetrahydrofuran, dioxane, chlorobenzene, fluorobenzene or solvent mixtures comprising one or more solvents like e.g. THF/toluene and optionally water. Most preferred is THF, or THF/water.
Advantageously, the polymerisation is carried out in presence of
a) palladium(ll) acetate, or Pd2(dba)3, (tris(dibenzylideneacetone)dipalladium(O)) and an organic phosphine A-1 to A-13,
b) LiOH, or LiOHxH20; and
c) THF, and optionally water. If the monohydrate of LiOH is used, no water needs to be added.
Most preferred the polymerisation is carried out in presence of a te, or Pd2(dba)3 (tris(dibenzylideneacetone)dipalladium(O)) and
Figure imgf000023_0001
b) LiOHxH20; and
c) THF. The palladium catalyst is present in an amount of preferably about 0.5 mol-%, based on the equivalents of the (hetero)aromatic compound(s) used. The amount of phosphines or phosphonium salts in the reaction mixture is preferably about 2 mol-%, based on the equivalents of the (hetero)aromatic compound(s) used. The preferred ratio of Pd:phosphine is about 1 :4. Preferably the polymerization reaction is conducted under inert conditions in the absence of oxygen. Nitrogen and more preferably argon are used as inert gases.
The process described in WO2010/136352 is suitable for large-scale applications, is readily accessible and convert starting materials to the respective polymers in high yield, with high purity and high selectivity. The process can provide polymers having weight average molecular weights of at least 10,000, more preferably at least 20,000, most preferably at least 30,000. The at present most preferred polymers have a weight average molecular weight of 30,000 to 80,000 Daltons. Molecular weights are determined according to high- temperature gel permeation chromatography (HT-GPC) using polystyrene standards. The polymers preferably have a polydispersibility of 1.01 to 10, more preferably 1.1 to 3.0, most preferred 1.5 to 2.5.
If desired, a monofunctional aryl halide or aryl boronate, such as, for example,
Figure imgf000023_0002
Figure imgf000024_0001
such reactions, which will result in the formation of a terminal aryl group.
It is possible to control the sequencing of the monomeric units in the resulting copolymer by controlling the order and composition of monomer feeds in the Suzuki reaction.
The polymers of the present invention can also be sythesized by the Stille coupling (see, for example, Babudri et al, J. Mater. Chem., 2004, 14, 11-34; J. K. Stille, Angew. Chemie Int. Ed. Engl. 1986, 25, 508). To prepare polymers corresponding to formula VII a dihalo-
10 10
X -A— X
genide of formula is reacted with a compound of formula X -COM -X y mi\/iJ y
or a dihalogenide of formula is reacted with a compound of formula
X -A— X 1 1'
wherein X11' is a group -SnR20 R208 R209 anc| χιο js as defined above, in an inert solvent at a temperature in range from 0°C to 200°C in the presence of a palladium- containing catalyst, wherein R207, R208 and R209 are identical or different and are H or Ci- Cealkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or unbranched. It must be ensured here that the totality of all monomers used has a highly balanced ratio of organotin functions to halogen functions. In addition, it may prove advantageous to remove any excess reactive groups at the end of the reaction by end-capping with monofunctional reagents. In order to carry out the process, the tin compounds and the halogen compounds are preferably introduced into one or more inert organic solvents and stirred at a temperature of from 0 to 200°C, preferably from 30 to 170°C for a period of from 1 hour to 200 hours, preferably from 5 hours to 150 hours. The crude product can be purified by methods known to the person skilled in the art and appropriate for the respective polymer, for example repeated re-precipitation or even by dialysis.
Suitable organic solvents for the process described are, for example, ethers, for example diethyl ether, dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, dioxolane, diisopropyl ether and tert-butyl methyl ether, hydrocarbons, for example hexane, isohexane, heptane, cyclohexane, benzene, toluene and xylene, alcohols, for example methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, 1-butanol, 2-butanol and tert- butanol, ketones, for example acetone, ethyl methyl ketone and isobutyl methyl ketone, amides, for example dimethylformamide (DMF), dimethylacetamide and N- methylpyrrolidone, nitriles, for example acetonitrile, propionitrile and butyronitrile, and mixtures thereof. The palladium and phosphine components should be selected analogously to the description for the Suzuki variant.
Alternatively, the polymers of the present invention can also be synthesized by the Negishi reaction using a zinc reagent A-(ZnX12)2, wherein X12 is halogen and halides, and COM1- (X23)2, wherein X23 is halogen or triflate, or using A-(X23)2 and COM1-(ZnX23)2. Reference is, for example, made to E. Negishi et al., Heterocycles 18 (1982) 1 17-22.
Alternatively, the polymers of the present invention can also be synthesized by the Hiyama reaction using a organosilicon reagent A-(SiR210R211 R212)2, wherein R 1°, R2i i and R 1 are identical or different and are halogen, or Ci-C6alkyl, and COM1-(X23)2, wherein X23 is halogen or triflate, or using A-(X23)2 and COM1-(SiR210R211R212)2. Reference is, for example, made to T. Hiyama et al., Pure Appl. Chem. 66 (1994) 1471-1478 and T. Hiyama et al., Synlett (1991) 845-853.
Homopolymers of the type (A)n can be obtained via Yamamoto coupling of dihalides
10
X -A— X 10
where X10 is halogen, preferably bromide. Alternatively homopolymers of
10
X -A— X 10 the type (A)n can be obtained via oxidative polymerization of units where X10 is hydrogen, e.g. with FeC as oxidizing agent.
Figure imgf000025_0001
(V) are intermediates in the production of the polymers of the present invention, are new and form a further subject of the present invention, a, a', b, b', c, c', d, d', Y, Ar1, Ar1', Ar2, Ar2', Ar3, Ar3', Ar4 and Ar4' are as defined in claim 1 , and X is halogen, especially Br, or J, ZnX12, - SnR^R^F^og, wherein R2°7, R2oe and R209 are identical or different and are H or Ci- Cealkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or unbranched and X12 is a halogen atom, very especially I, or Br; or -
OS(0)2CF3, -OS(0)2-aryl, especially
Figure imgf000025_0002
-OS(0)2CH3, -B(OH)2, -B(OY1)2,
Figure imgf000025_0003
-BF4Na, or -BF4K, wherein Y1 is independently in each occurrence a Ci-Cioalkyl group and Y2 is independently in each occurrence a C2- Cioalkylene group, such as -CY3Y -CYSY6-, or -CY7Y8-CY9Y1o- CY11Y12-, wherein Y3, Y4, Y5, Y6, Y7, Y8, Y9, γιο, γι ι and Y12 are independently of each other hydrogen, or a Ci- Cioalkyl group, especially -C(CH3)2C(CH3)2-, -C(CH3)2CH2C(CH3)2-, or -CH2C(CH3)2CH2- and Y13 and Y14 are independently of each other hydrogen, or a Ci-Cioalkyl group.
X is preferably different from a halogen atom.
Examples of compounds of formula V are shown below:
Figure imgf000026_0001
(Vb), wherein X is as defined above, T1 and T2 are independently of each other hydrogen, or Ci-C2salkyl, especially hydrogen; R1 is a Ci-C38alkyl group, especially a Ce-C36alkyl group,
R105 and R105' are independently of each other hydrogen, halogen, cyano, Ci-C2salkyl or Ci- C25alkoxy, especially hydrogen or Ci-C2salkyl.
Examples of compounds of formula V are shown below:
Figure imgf000026_0002
Figure imgf000027_0001
The polymers, wherein R1 and/or R2 are hydrogen can be obtained by using a protecting group which can be removed after polymerization. Reference is made, for example, to EP- A-0648770, EP-A-0648817, EP-A-0742255, EP-A-0761772, WO98/32802, W098/45757, WO98/58027, WO99/0151 1 , WOOO/17275, WOOO/39221 , WOOO/63297 and E P-A- 1086984, which describe the basic procedural method. Conversion of the pigment precursor into its pigmentary form is carried out by means of fragmentation under known conditions, for example thermally, optionally in the presence of an additional catalyst, for example the catalysts described in WOOO/36210.
O
An example of such a protecting group is group of formula , wherein L is any
O - L
desired group suitable for imparting solubility.
L is preferably a group of formula
Figure imgf000027_0002
Figure imgf000027_0003
or wherein Z1, Z2 and Z3 are independently of each other Ci-C6alkyl,
Z4 and Z8 are independently of each other Ci-C6alkyl, Ci-C6alkyl interrupted by oxygen, sulfur or N(Z12)2, or unsubstituted or Ci-C6alkyl-, Ci-C6alkoxy-, halo-, cyano- or nitro- substituted phenyl or biphenyl,
Z5, Z6 and Z7 are independently of each other hydrogen or Ci-C6alkyl, Z9 is hydrogen, Ci-C6alkyl or a group of formula
Figure imgf000028_0001
, or
O
Z10 and Z11 are each independently of the other hydrogen, Ci-C6alkyl, Ci-C6alkoxy, halogen, cyano, nitro, N(Z12)2, or unsubstituted or halo-, cyano-, nitro-, Ci-C6alkyl- or
Ci-C6alkoxy-substituted phenyl,
Z12 and Z13 are Ci-C6alkyl, Z14 is hydrogen or Ci-C6alkyl, and Z15 is hydrogen, Ci-C6alkyl, or unsubstituted or Ci-C6alkyl-substituted phenyl,
Q* is p,q-C2-C6alkylene unsubstituted or mono- or poly-substituted by Ci-C6alkoxy, Ci-C6alkylthio or C2-Ci2dialkylamino, wherein p and q are different position numbers, X" is a hetero atom selected from the group consisting of nitrogen, oxygen and sulfur, m' being the number 0 when X" is oxygen or sulfur and m being the number 1 when X" is nitrogen, and
L1 and L2 are independently of each other unsubstituted or mono- or poly-Ci-Ci2alkoxy-, -Ci-Ci2alkylthio-, -C2-C24dialkylamino-, -C6-Ci2aryloxy-, -C6-Ci2arylthio-,
-C7-C24alkylarylamino- or -Ci2-C24diarylamino-substituted Ci-C6alkyl or [-(p',q -
C2-C6alkylene)-Z-]n -Ci-C6alkyl , n' being a number from 1 to 1000, p' and q' being different position numbers, each Z independently of any others being a hetero atom oxygen, sulfur or Ci-Ci2alkyl-substituted nitrogen, and it being possible for C2-C6alkylene in the repeating [-C2-C6alkylene-Z-] units to be the same or different,
and Li and l_2 may be saturated or unsaturated from one to ten times, may be uninterrupted or interrupted at any location by from 1 to 10 groups selected from the group consisting of -(C=0)- and -C6H4-, and may carry no further substituents or from 1 to 10 further substitu- ents selected from the group consisting of halogen, cyano and nitro. Most preferred L is a
O CH3
-o- -CH3
group of formula
The synthesis of the compounds of formula can be done in analogy to the meth ods described in C. Greenhalgh et al., Dyes and Pigments 1 (1980) 103-120 and G Hallas et al. Dyes and Pigments 48 (2001) 121-132.
Rr Δ pr
The synthesis of the compounds of formula is described in WO08/000664, and WO09/047104, or can be done in analogy to the methods described therein. The syn-
Rr Δ pr
thesis of N-aryl substituted compounds of formula can be done in analogy to the methods described in US-A-5,354,869 and WO03/022848. Halogen is fluorine, chlorine, bromine and iodine.
Ci-C25alkyl (Ci-Ciealkyl) is typically linear or branched, where possible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, 1 ,1 ,3,3-tetramethylpentyl, n-hexyl, 1 -methyl hexyl, 1 ,1 ,3,3,5,5- hexamethylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3-methyl- heptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl. Ci-Cealkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl-propyl, n- hexyl, n-heptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2-ethylhexyl. Ci-C4alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.-butyl.
C2-Ciealkenyl groups are straight-chain or branched alkenyl groups, such as e.g. vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2- enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.
C2-iealkynyl is straight-chain or branched and preferably C2-ealkynyl, which may be unsubstituted or substituted, such as, for example, ethynyl, 1-propyn-3-yl, 1-butyn-4-yl,
1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1 ,4-pentadiyn-3-yl, 1 ,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1-yl, trans-3-methyl-2-penten-4-yn-1-yl, 1 ,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn-9-yl, 1-decyn-10-yl, or 1-tetracosyn-24-yl.
Ci-C25alkoxy groups (Ci-Ciealkoxy groups) are straight-chain or branched alkoxy groups, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecy- loxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy and octade- cyloxy. Examples of Ci-Cealkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, 2,2-dimethylpropoxy, n-hexoxy, n-heptoxy, n-octoxy, 1 , 1 ,3,3-tetramethylbutoxy and 2-ethylhexoxy, preferably Ci- C4alkoxy such as typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy. The term "alkylthio group" means the same groups as the alkoxy groups, except that the oxygen atom of the ether linkage is replaced by a sulfur atom.
Ci-Ci8perfluoroalkyl, especially Ci-C4perfluoroalkyl, is a branched or unbranched radical such as for example -CF3, -CF2CF3, -CF2CF2CF3, -CF(CF3)2, -(CF2)3CF3, and -C(CF3)3.
The term "carbamoyl group" is typically a Ci-i8carbamoyl radical, preferably Ci-ecarbamoyl radical, which may be unsubstituted or substituted, such as, for example, carbamoyl, me- thylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, tert-butylcarbamoyl, dimethylcarbamoy- loxy, morpholinocarbamoyl or pyrrolidinocarbamoyl.
C5-Ci2cycloalkyl is typically cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted or substituted. The cycloalkyi group, in particular a cyclohexyl group, can be condensed one or two times by phenyl which can be substituted one to three times with Ci-C4-alkyl, halogen and cyano. Examples of such condensed
Figure imgf000030_0001
R155 and R156 are independently of each other Ci-Ce-alkyl, Ci-Ce-alkoxy, halogen and cyano, in particular hydrogen.
C6-C24aryl (C6-Ci8aryl) is typically phenyl, indenyl, azulenyl, naphthyl, biphenyl, as- indacenyl, s-indacenyl, acenaphthylenyl, fluorenyl, phenanthryl, fluoranthenyl, triphenlenyl, chrysenyl, naphthacen, picenyl, perylenyl, pentaphenyl, hexacenyl, pyrenyl, or anthracenyl, preferably phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, 9-phenanthryl, 2- or 9-fluorenyl, 3- or 4-biphenyl, which may be unsubstituted or substituted. Examples of C6-Ci2aryl are phenyl, 1-naphthyl, 2-naphthyl, 3- or 4-biphenyl, 2- or 9-fluorenyl or 9-phenanthryl, which may be unsubstituted or substituted. C7-C25aralkyl is typically benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, co-phenyl-butyl, ω,ω-dimethyl-co-phenyl-butyl, ω-phenyl-dodecyl, ω-phenyl-octadecyl, ω-phenyl-eicosyl or ω-phenyl-docosyl, preferably C7-Ci8aralkyl such as benzyl, 2-benzyl-2- propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, co-phenyl-butyl, ω,ω-dimethyl-co-phenyl-butyl, ω-phenyl-dodecyl or ω-phenyl-octadecyl, and particularly preferred C7-Ci2aralkyl such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, or ω,ω-dimethyl-co-phenyl-butyl, in which both the aliphatic hydrocarbon group and aromatic hydrocarbon group may be unsubstituted or substituted. Preferred examples are benzyl, 2- phenylethyl, 3-phenylpropyl, naphthylethyl, naphthylmethyl, and cumyl. Heteroaryl is typically C2-C2oheteroaryl, i.e. a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically an unsaturated heterocyclic group with five to 30 atoms having at least six conjugated π-electrons such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrro- lyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indol- izinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl, chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbazolyl, carbolinyl, ben- zotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl or phenoxazinyl, which can be unsubstituted or substituted.
Possible substituents of the above-mentioned groups are Ci-Cealkyl, a hydroxyl group, a mercapto group, Ci-Cealkoxy, Ci-Cealkylthio, halogen, halo-Ci-Cealkyl, a cyano group, a carbamoyl group, a nitro group or a silyl group, especially Ci-Cealkyl, Ci-Cealkoxy, Ci- Cealkylthio, halogen, halo-Ci-Cealkyl, or a cyano group.
Ci-Ciealkyl interrupted by one or more O is, for example, (CH2CH20)i-g-Rx, where Rx is H or Ci-Ci0alkyl, CH2-CH(ORy')-CH2-0-Ry, where Ry is Ci-Ci8alkyl, and Ry' embraces the same definitions as Ry or is H.
If a substituent, such as, for example R3, occurs more than one time in a group, it can be different in each occurrence.
A mixture containing a polymer of the present invention results in a semi-conducting layer comprising a polymer of the present invention (typically 5% to 99.9999% by weight, especially 20 to 85 % by weight) and at least another material. The other material can be, but is not restricted to a fraction of the same polymer of the present invention with different mo- lecular weight, another polymer of the present invention, a semi-conducting polymer, organic small molecules, carbon nanotubes, a fullerene derivative, inorganic particles (quantum dots, quantum rods, quantum tripods, T1O2, ZnO etc.), conductive particles (Au, Ag etc.), insulator materials like the ones described for the gate dielectric (PET, PS etc.). The polymers of the present invention can be blended with small molecules described, for example, in WO2009/047104, PCT/EP2010/053655, WO09/047104, US6,690,029, WO2007082584, and WO2008107089:
WO2007082584:
Figure imgf000031_0001
31
Figure imgf000032_0001
Figure imgf000033_0001
wherein one of Y1' and Y2' denotes -CH= or =CH- and the other denotes -X*-,
one of Y3' and Y4' denotes -CH= or =CH- and the other denotes -X*-,
X* is -0-, -S-, -Se- or -NR'"-,
R* is cyclic, straight-chain or branched alkyl or alkoxy having 1 to 20 C-atoms, or aryl having 2-30 C-atoms, all of which are optionally fluorinated or perfluorinated,
R' is H, F, CI, Br, I, CN, straight-chain or branched alkyl or alkoxy having 1 to 20 C-atoms and optionally being fluorinated or perfluorinated, optionally fluorinated or perfluorinated aryl having 6 to 30 C-atoms, or CO2R", with R" being H, optionally fluorinated alkyl having 1 to 20 C-atoms, or optionally fluorinated aryl having 2 to 30 C-atoms,
R'" is H or cyclic, straight-chain or branched alkyl with 1 to 10 C-atoms, y is 0, or 1 , x is 0, or 1.
Figure imgf000033_0002
The polymer can contain a small molecule, or a mixture of two, or more small molecule compounds. Accordingly, the present invention also relates to an organic semiconductor material, layer or component, comprising a polymer according to the present invention. The polymers of the invention can be used as the semiconductor layer in semiconductor devices. Accordingly, the present invention also relates to semiconductor devices, comprising a polymer of the present invention, or an organic semiconductor material, layer or component. The semiconductor device is especially an organic photovoltaic (PV) device (solar cell), a photodiode, or an organic field effect transistor.
The polymers of the invention can be used alone or in combination as the organic semiconductor layer of the semiconductor device. The layer can be provided by any useful means, such as, for example, vapor deposition (for materials with relatively low molecular weight) and printing techniques. The compounds of the invention may be sufficiently solu- ble in organic solvents and can be solution deposited and patterned (for example, by spin coating, dip coating, ink jet printing, gravure printing, flexo printing, offset printing, screen printing, microcontact (wave)-printing, drop or zone casting, or other known techniques).
The polymers of the invention can be used in integrated circuits comprising a plurality of OTFTs, as well as in various electronic articles. Such articles include, for example, radio- frequency identification (RFID) tags, backplanes for flexible displays (for use in, for example, personal computers, cell phones, or handheld devices), smart cards, memory devices, sensors (e.g. light-, image-, bio-, chemo-, mechanical- or temperature sensors), especially photodiodes, or security devices and the like.
A further aspect of the present invention is an organic semiconductor material, layer or component comprising one or more polymers of the present invention. A further aspect is the use of the polymers or materials of the present invention in an organic photovoltaic (PV) device (solar cell), a photodiode, or an organic field effect transistor (OFET). A further as- pect is an organic photovoltaic (PV) device (solar cell), a photodiode, or an organic field effect transistor (OFET) comprising a polymer or material of the present invention.
The polymers of the present invention are typically used as organic semiconductors in form of thin organic layers or films, preferably less than 30 microns thick. Typically the semicon- ducting layer of the present invention is at most 1 micron (=1 μηη) thick, although it may be thicker if required. For various electronic device applications, the thickness may also be less than about 1 micron thick. For example, for use in an OFET the layer thickness may typically be 100 nm or less. The exact thickness of the layer will depend, for example, upon the requirements of the electronic device in which the layer is used.
For example, the active semiconductor channel between the drain and source in an OFET may comprise a layer of the present invention.
An OFET device according to the present invention preferably comprises:
- a source electrode, - a drain electrode,
- a gate electrode,
- a semiconducting layer,
- one or more gate insulator layers, and
- optionally a substrate, wherein the semiconductor layer comprises one or more polymers of the present invention.
The gate, source and drain electrodes and the insulating and semiconducting layer in the OFET device may be arranged in any sequence, provided that the source and drain elec- trade are separated from the gate electrode by the insulating layer, the gate electrode and the semiconductor layer both contact the insulating layer, and the source electrode and the drain electrode both contact the semiconducting layer.
Preferably the OFET comprises an insulator having a first side and a second side, a gate electrode located on the first side of the insulator, a layer comprising a polymer of the present invention located on the second side of the insulator, and a drain electrode and a source electrode located on the polymer layer.
The OFET device can be a top gate device or a bottom gate device.
Suitable structures and manufacturing methods of an OFET device are known to the person skilled in the art and are described in the literature, for example in WO03/052841.
The gate insulator layer may comprise for example a fluoropolymer, like e.g. the commer- cially available Cytop 809M®, or Cytop 107M® (from Asahi Glass). Preferably the gate insulator layer is deposited, e.g. by spin-coating, doctor blading, wire bar coating, spray or dip coating or other known methods, from a formulation comprising an insulator material and one or more solvents with one or more fluoro atoms (fluorosolvents), preferably a per- fluorosolvent. A suitable perfluorosolvent is e.g. FC75® (available from Acros, catalogue number 12380). Other suitable fluoropolymers and fluorosolvents are known in prior art, like for example the perfluoropolymers Teflon AF® 1600 or 2400 (from DuPont), or Fluoro- pel® (from Cytonix) or the perfluorosolvent FC 43® (Acros, No. 12377).
The semiconducting layer comprising a polymer of the present invention may additionally comprise at least another material. The other material can be, but is not restricted to another polymer of the present invention, a semi-conducting polymer, a polymeric binder, organic small molecules different from a polymer of the present invention, carbon nano- tubes, a fullerene derivative, inorganic particles (quantum dots, quantum rods, quantum tripods, T1O2, ZnO etc.), conductive particles (Au, Ag etc.), and insulator materials like the ones described for the gate dielectric (PET, PS etc.). As stated above, the semiconductive layer can also be composed of a mixture of one or more polymers of the present invention and a polymeric binder. The ratio of the polymers of the present invention to the polymeric binder can vary from 5 to 95 percent. Preferably, the polymeric binder is a semicristalline polymer such as polystyrene (PS), high-density polyethylene (HDPE), polypropylene (PP) and polymethylmethacrylate (PMMA). With this technique, a degradation of the electrical performance can be avoided (cf. WO2008/001 123A1).
The polymers of the present invention are advantageously used in organic photovoltaic (PV) devices (solar cells). Accordingly, the invention provides PV devices comprising a polymer according to the present invention. A device of this construction will also have rectifying properties so may also be termed a photodiode. Photoresponsive devices have application as solar cells which generate electricity from light and as photodetectors which measure or detect light.
The structure of organic photovoltaic devices (solar cells) is, for example, described in C. Deibel et al. Rep. Prog. Phys. 73 (2010) 096401 and Christoph Brabec, Energy Environ. Sci 2. (2009) 347-303. The PV device comprise in this order:
(a) a cathode (electrode),
(b) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride,
(c) a photoactive layer,
(d) optionally a smoothing layer,
(e) an anode (electrode),
(f) a substrate.
The photoactive layer comprises the polymers of the present invention. Preferably, the photoactive layer is made of a conjugated polymer of the present invention, as an electron donor and an acceptor material, like a fullerene, particularly a functionalized fullerene
PCBM, as an electron acceptor. As stated above, the photoactive layer may also contain a polymeric binder. The ratio of the polymers of formula I to the polymeric binder can vary from 5 to 95 percent. Preferably, the polymeric binder is a semicristalline polymer such as polystyrene (PS), high-density polyethylene (HDPE), polypropylene (PP) and polymethyl- methacrylate (PMMA).
For heterojunction solar cells the active layer comprises preferably a mixture of a polymer of the present invention and a fullerene, such as [60]PCBM (= 6,6-phenyl-C6i-butyric acid methyl ester), or [70]PCBM, in a weight ratio of 1 :1 to 1 :3. The fullerenes useful in this in- vention may have a broad range of sizes (number of carbon atoms per molecule). The term fullerene as used herein includes various cage-like molecules of pure carbon, including Buckminsterfullerene (C6o) and the related "spherical" fullerenes as well as carbon nano- tubes. Fullerenes may be selected from those known in the art ranging from, for example, C2o-Ciooo- Preferably, the fullerene is selected from the range of C6o to C96. Most preferably the fullerene is C60 or C70, such as [60]PCBM, or [70]PCBM. It is also permissible to utilize chemically modified fullerenes, provided that the modified fullerene retains acceptor-type and electron mobility characteristics. The acceptor material can also be a material selected from the group consisting of any semi-conducting polymer, such as, for example, a polymer of the present invention, provided that the polymers retain acceptor-type and electron mo- bility characteristics, organic small molecules, carbon nanotubes, inorganic particles (quantum dots, quantum rods, quantum tripods, ΤΊΟ2, ZnO etc.).
The photoactive layer is made of a polymer of the present invention as an electron donor and a fullerene, particularly functionalized fullerene PCBM, as an electron acceptor. These two components are mixed with a solvent and applied as a solution onto the smoothing layer by, for example, the spin-coating method, the drop casting method, the Langmuir- Blodgett ("LB") method, the ink jet printing method and the dripping method. A squeegee or printing method could also be used to coat larger surfaces with such a photoactive layer. Instead of toluene, which is typical, a dispersion agent such as chlorobenzene is preferably used as a solvent. Among these methods, the vacuum deposition method, the spin-coating method, the ink jet printing method and the casting method are particularly preferred in view of ease of operation and cost. In the case of forming the layer by using the spin-coating method, the casting method and inkjet printing method, the coating can be carried out using a solution and/or dispersion prepared by dissolving, or dispersing the composition in a concentration of from 0.01 to 90% by weight in an appropriate organic solvent such as benzene, toluene, xylene, tetra- hydrofurane, methyltetrahydrofurane, Ν,Ν-dimethylformamide, acetone, acetonitrile, ani- sole, dichloromethane, dimethylsulfoxide, chlorobenzene, 1 ,2-dichlorobenzene and mixtures thereof.
The photovoltaic (PV) device can also consist of multiple junction solar cells that are processed on top of each other in order to absorb more of the solar spectrum. Such structures are, for example, described in App. Phys. Let. 90, 143512 (2007), Adv. Funct. Mater. 16, 1897-1903 (2006), WO2004/112161 and Christoph Brabec, Energy Environ. Sci 2. (2009) 347-303.
A so called 'tandem solar cell' comprise in this order:
(a) a cathode (electrode),
(b) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride,
(c) a photoactive layer,
(d) optionally a smoothing layer,
(e) a middle electrode (such as Au, Al, ZnO, T1O2 etc.)
(f) optionally an extra electrode to match the energy level,
(g) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride,
(h) a photoactive layer,
(i) optionally a smoothing layer,
0) an anode (electrode),
(k) a substrate.
The PV device can also be processed on a fiber as described, for example, in
US20070079867 and US 20060013549. Due to their excellent self-organising properties the materials or films comprising the polymers of the present invention can also be used alone or together with other materials in or as alignment layers in LCD or OLED devices, as described for example in
US2003/0021913.
In a further embodiment the present invention relates to compounds of the formula
Figure imgf000038_0001
wherein a, a', b, b', c, c', d, d', Y, Ar1, Ar1 ', Ar2, Ar2', Ar3, Ar3', Ar4 and Ar4' are as defined above,
R10 and R10' are independently of each other hydrogen, halogen, cyano, Ci-C2salkyl, Ci- C25alkoxy, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C2oheteroaryl, C2- ,
Figure imgf000038_0002
wherein R22 to R26 and R29 to R58 represent independently of each other H, halogen, cyano, Ci-C25alkyl, Ci-C2salkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6- C24aryl which is substituted by G, C2-C2oheteroaryl, C2-C2oheteroaryl which is substituted by G, a C4-Ci8cycloalkyl group, a C4-Ci8cycloalkyl group, which is substituted by G, C2- Ciealkenyl, C2-Ci8alkynyl, Ci-Ciealkoxy, Ci-Ciealkoxy which is substituted by E and/or interrupted by D, C7-C25aralkyl, or C7-C2saralkyl, which is substituted by G,
R27 and R28 are independently of each other hydrogen, Ci-C2salkyl, halogen, cyano or C7- C25aralkyl, or R27 and R28 together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the thienyl residue and which may both have up to 25 carbon atoms,
D is -CO-, -COO-, -S-, -0-, or -NR112-,
E is Ci-C8thioalkoxy, Ci-C8alkoxy, CN, -NR112R113, -CONR112R113, or halogen,
G is E, or Ci-Ciealkyl, and
R112 and R113 are independently of each other H; Ce-Ciearyl; Ce-Ciearyl which is substituted by Ci-Ciealkyl, or Ci-Ciealkoxy; Ci-Ciealkyl; or Ci-Ciealkyl which is interrupted by -0-, with the proviso that Ar1 and Ar1' are not a group of formula (XVa), if b, b', c, c', d and d' are 0 and R10 and R10' are independently of each other hydrogen, halogen, Ci-Cealkyl, or Ci- C25alkoxy.
In a preferred embodiment of the present invention Ar1 and Ar1 ' are not a group of formula XVa, if b, b', c, c', d and d' are 0.
In a preferred embodiment of the present invention R10 and R10' are independently of each other cyano, especially a group of one of the formulae IVa to IVj.
In a preferred embodiment of the present invention R10 and R10' are independently of each other cyano, especially a group of one of the formulae IVa to IVj, if Ar1 and Ar1' are a group of formula XVa, b, b', c, c', d and d' are 0.
Figure imgf000039_0001
Compounds of the formula are more preferred '), wherein
Y is a group of formula
Figure imgf000039_0002
U1 is O, S, or NR1;
U2 is O, S, or NR2;
T1 and T2 are independently of each other hydrogen, halogen, hydroxyl, cyano, -COOR103, - OCOR103, -NR11 COR103, -CONR11 R113, -OR103', -SR103', -SOR103', -S02R103', - NR112S02R103', -NR112R113, Ci-C25alkyl, which which may be substituted by E and/or interrupted by D, C5-Ci2cycloalkyl, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; C7-C2sarylalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2- C2oheteroaryl, or C2-C2oheteroaryl which is substituted by G;
R1 and R2 may be the same or different and are selected from hydrogen, a Ci-Ciooalkyl group, -COOR103, -COR103, a Ci-Ciooalkyl group which is substituted by one or more halogen atoms, hydroxyl groups, nitro groups, -CN, or Ce-Ciearyl groups and/or interrupted by - 0-, -COO-, -OCO-, or -S-; a C7-Ciooarylalkyl group, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; a carbamoyl group, C5-Ci2cycloalkyl, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; a C6-C24aryl group, in particular phenyl or 1- or 2-naphthyl, which can be substituted one to three times with Ci- Cealkyl, Ci-Cethioalkoxy, and/or Ci-Cealkoxy, or pentafluorophenyl;
a is 1 , 2, or 3, a' is 1 , 2, or 3; wherein Ar1 and Ar1' are independently of each other a group of formula (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), or (XVh) (as defined in claim 1); Rio, Rio', 103, R103', Ri i2_ R113. D, E and G are as defined above.
Ar1 and Ar1 ' may be different, but are preferably the same. Ar1 and Ar1' are independently of each other a group of formula (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), or (XVh), preferably a group of formula (XVa), (XVb), (XVc), (XVd) or (XVe), more preferably a group of formula (XVa), (XVd) or (XVe), most preferably a group of formula (XVa).
Figure imgf000040_0001
Compounds of formula (III") are even more preferred, wherein a is 1 , or 2, especially 1 ; a' is 1 , or 2, especially 1 ; b is 1 , 2, or 3; b' is 1 , 2, or 3; wherein Y, Ar1 and Ar1' are as defined above; and Ar2 and Ar2' are a group of formula (Xa), (Xc), (Xg), (Xh), (Xm), (Xn), (Xo), (Xp), (Xy), (Xle), (Xlf), (XII), or (Xlm).
Examples of preferred compounds are shown below:
Figure imgf000040_0002
Figure imgf000041_0001
o o o o o
, and o o o
Advantageously, the compound of formula III, or an organic semiconductor material, layer or component, comprising the compound of formula III can be used in organic photovoltaics (solar cells) and photodiodes, or in an organic field effect transistor (OFET).
A mixture containing the compound of formula III results in a semi-conducting layer comprising the compound of formula III (typically 5% to 99.9999% by weight, especially 20 to 85 % by weight) and at least another material. The other material can be, but is not restricted to another compound of formula III, a polymer of the present invention, a semi-conducting polymer, a non-conductive polymer, organic small molecules, carbon nanotubes, a fullerene derivative, inorganic particles (quantum dots, quantum rods, quantum tripods, ΤΊΟ2, ZnO etc.), conductive particles (Au, Ag etc.), insulator materials like the ones described for the gate dielectric (PET, PS etc.).
Accordingly, the present invention also relates to an organic semiconductor material, layer or component, comprising a compound of formula III and to a semiconductor device, comprising a compound of formula III and/or an organic semiconductor material, layer or com- ponent.
The semiconductor is preferably an organic photovoltaic (PV) device (solar cell), a photodi- ode, or an organic field effect transistor. The structure and the components of the OFET device has been described in more detail above.
Accordingly, the invention provides organic photovoltaic (PV) devices (solar cells) comprising a compound of the formula III.
The PV device comprise in this order:
(a) a cathode (electrode),
(b) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride,
(c) a photoactive layer,
(d) optionally a smoothing layer,
(e) an anode (electrode),
(f) a substrate. The photoactive layer comprises the compounds of the formula III. Preferably, the photoactive layer is made of a compound of the formula III, as an electron donor and an acceptor material, like a fullerene, particularly a functionalized fullerene PCBM, as an electron acceptor. As stated above, the photoactive layer may also contain a polymeric binder. The ratio of the small molecules of formula III to the polymeric binder can vary from 5 to 95 percent. Preferably, the polymeric binder is a semicristalline polymer such as polystyrene (PS), high-density polyethylene (HDPE), polypropylene (PP) and polymethylmethacrylate (PMMA). The fullerenes useful in this invention may have a broad range of sizes (number of carbon atoms per molecule). The term fullerene as used herein includes various cage-like molecules of pure carbon, including Buckminsterfullerene (C6o) and the related "spherical" fullerenes as well as carbon nanotubes. Fullerenes may be selected from those known in the art ranging from, for example, C2o-Ciooo- Preferably, the fullerene is selected from the range of C6o to C96. Most preferably the fullerene is C60 or C70, such as [60]PCBM, or
[70]PCBM. It is also permissible to utilize chemically modified fullerenes, provided that the modified fullerene retains acceptor-type and electron mobility characteristics. The acceptor material can also be a material selected from the group consisting of another compounds of formula III, or any semi-conducting polymer, such as, for example, a polymer of formula I, provided that the polymers retain acceptor-type and electron mobility characteristics, organic small molecules, carbon nanotubes, inorganic particles (quantum dots, quantum rods, quantum tripods, T1O2, ZnO etc.).
The photoactive layer is made of a compound of the formula III, as an electron donor and a fullerene, particularly functionalized fullerene PCBM, as an electron acceptor. These two components are mixed with a solvent and applied as a solution onto the smoothing layer by, for example, the spin-coating method, the drop casting method, the Langmuir-Blodgett ("LB") method, the ink jet printing method and the dripping method. A squeegee or printing method could also be used to coat larger surfaces with such a photoactive layer. Instead of toluene, which is typical, a dispersion agent such as chlorobenzene is preferably used as a solvent. Among these methods, the vacuum deposition method, the spin-coating method, the inkjet printing method and the casting method are particularly preferred in view of ease of operation and cost. In the case of forming the layer by using the spin-coating method, the casting method and inkjet printing method, the coating can be carried out using a solution and/or dispersion prepared by dissolving, or dispersing the composition in a concentration of from 0.01 to 90% by weight in an appropriate organic solvent such as benzene, toluene, xylene, tetra- hydrofurane, methyltetrahydrofurane, Ν,Ν-dimethylformamide, acetone, acetonitrile, ani- sole, dichloromethane, dimethylsulfoxide, chlorobenzene, 1 ,2-dichlorobenzene and mixtures thereof.
The photovoltaic (PV) device can also consist of multiple junction solar cells that are processed on top of each other in order to absorb more of the solar spectrum. Such structures are, for example, described in App. Phys. Let. 90, 143512 (2007), Adv. Funct. Mater. 16, 1897-1903 (2006), WO2004/112161 and Christoph Brabec, Energy Environ. Sci 2. (2009) 347-303.
A so called 'tandem solar cell' comprise in this order:
(a) a cathode (electrode),
(b) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride,
(c) a photoactive layer,
(d) optionally a smoothing layer,
(e) a middle electrode (such as Au, Al, ZnO, ΤΊΟ2 etc.)
(f) optionally an extra electrode to match the energy level,
(g) optionally a transition layer, such as an alkali halogenide, especially lithium fluoride,
(h) a photoactive layer,
(i) optionally a smoothing layer,
0) an anode (electrode),
(k) a substrate.
The PV device can also be processed on a fiber as described, for example, in
US20070079867 and US 20060013549. Due to their excellent self-organising properties the materials or films comprising the compounds of the formula III can also be used alone or together with other materials in or as alignment layers in LCD or OLED devices, as described for example in US2003/0021913.
An OFET device according to the present invention preferably comprises:
- a source electrode,
- a drain electrode,
- a gate electrode,
- a semiconducting layer,
- one or more gate insulator layers, and
- optionally a substrate, wherein the semiconductor layer comprises a compound of formula III.
The gate, source and drain electrodes and the insulating and semiconducting layer in the OFET device may be arranged in any sequence, provided that the source and drain elec- trade are separated from the gate electrode by the insulating layer, the gate electrode and the semiconductor layer both contact the insulating layer, and the source electrode and the drain electrode both contact the semiconducting layer.
Preferably the OFET comprises an insulator having a first side and a second side, a gate electrode located on the first side of the insulator, a layer comprising a compound of formula III located on the second side of the insulator, and a drain electrode and a source electrode located on the polymer layer.
The following examples are included for illustrative purposes only and do not limit the scope of the claims. Unless otherwise stated, all parts and percentages are by weight. Weight-average molecular weight (Mw) and polydispersity (Mw/Mn = PD) are determined by Heat Temperature Gel Permeation Chromatography (HT-GPC) [Apparatus: GPC PL 220 from Polymer laboratories (Church Stretton, UK; now Varian) yielding the responses from refractive index (Rl), Chromatographic conditions: Column: 3 "PLgel Olexis" column from Polymer Laboratories (Church Stretton, UK); with an average particle size of 13 im (dimensions 300 x 8 mm I.D.) Mobile phase: 1 ,2,4-trichlorobenzene purified by vacuum distillation and stabilised by butylhydroxytoluene (BHT, 200 mg/l), Chromatographic temperature: 150°C; Mobile phase flow: 1 ml/min; Solute concentration: about 1 mg/ml; Injection volume: 200 il; Detection: Rl, Procedure of molecular weight calibration: Relative calibration is done by use of a set of 10 polystyrene calibration standards obtained from Polymer Laboratories (Church Stretton, UK) spanning the molecular weight range from 1 Ό30Ό00 Da - 5Ό50 Da, i. e., PS 1 Ό30Ό00, PS 1 '460Ό00, PS 1 Ό75Ό00, PS 560Ό00, PS 330Ό00, PS 96Ό00, PS 52Ό00, PS 30'300, PS 10Ί00, PS 5Ό50 Da. A polynomic calibration is used to calculate the molecular weight.
All polymer structures given in the examples below are idealized representations of the polymer products obtained via the polymerization procedures described. If more than two components are copolymerized with each other sequences in the polymers can be either alternating or random depending on the polymerisation conditions.
Examples
Figure imgf000044_0001
Using a Dean Stark apparatus, hydroquinone (1 g, 9.09 mmol) and mandelic acid (2.76 g 18.18 mmol) were dissolved in 1 ,2,4-trichlorobenzene (20 ml) and stirred for 12 h at 200 °C. After cooling to 60 °C, nitrobenzene (2.3 ml) was added and the mixture was stirred for another hour at 200 °C. After cooling to room temperature, 50 ml methanol were added. A precipitate formed, which was filtered off, washed with methanol and dried in air. 3a was obtained as a yellow solid (2.32 g, 75 %). 1H-NMR (300 MHz, CDCI3): δ = 7.80 (d, aromatic, 4H), 7.55 (t, aromatic H, 4H), 6.89 (t, aromatic H, 2H), 6.61 (s, aromatic, 2H). UV/Vis (di- chloromethane): 469 nm. Fluorescence (dichloromethane): 600 nm. ε(469) = 35 000 L mol- 1 cm 1.
Figure imgf000045_0001
The same procedure as described for compound 3a was used except that mandelic acid was replaced by 4'-bromo-mandelic acid. 3b was obtained as a dark greenish solid (65 %), which was only little soluble in common solvents at room temperature, (m.p. above 300 °C). Anal. Calculated for C22HioBr204: C, 53.05 %; H, 2.02 %. Found: C, 52.80 %; H, 3.08 %. UVA/is (dichloromethane):
Figure imgf000045_0002
at 483 nm. Fluorescence (dichloromethane): 586 nm. (3c).
Figure imgf000045_0003
t that mandelic acid was replaced by 3-bromo-5-methoxy-mandelic acid. 3c was obtained as a dark greenish solid (65 %), which was only little soluble in common solvents at room temperature, (m.p. above 300 °C). Anal. Calculated for C24Hi4Br206: C, 51.64 %; H, 2.53 %. Found: C, 51.10 %; H, 3.01 %. UVA/is (dichloromethane):
Figure imgf000045_0004
at 391 , 477 nm. Fluorescence (dichloromethane): 610 nm.
3,7-Bis(3-bromo-4,5-dimethoxyphenyl)benzo[1 ,2-b:4,5-b']difuran-2,6-dione (3d).
Figure imgf000045_0005
The same procedure as described for compound 3a was used except that mandelic acid was replaced by 3-bromo-4,5-dimethoxy-mandelic acid. 3d was obtained as a dark solid (70 %), which was only little soluble in common solvents at room temperature, (m.p. above 300 °C). Anal. Calculated for C26Hi8Br208: C, 50.51 %; H, 2.93 %. Found: C, 50.00 %; H, 3.52 %. UVA/is (dichloromethane):
Figure imgf000045_0006
at 382, 521 nm. Fluorescence (dichloromethane): 606 nm.
Example 2
Figure imgf000046_0001
4,5-dimethoxy-mandelic acid (1d) (1.20 g, 5.66 mmol), 5-hydroxy-3-phenylbenzofuran- 2(3H)-one (4a) (1.27 g, 5.66 mmol), p-toluenesulphonric acid (1.27 g, 6.79 mmol) in 1 ,2,4- trichlorobenzene (20 ml) were heated to 80 °C and stirred for 6 h. The mixture was allowed to cool to 40 °C, and nitrobenzene (2 ml) was added. The temperature was raised to 100 °C and stirred for a further h. Methanol (5 ml) was added. The precipitated product was filtered off and recrystallized from dichloromethane/methanol, giving a dark red solid (1.47 g, 65 %). 1 H-NMR (300 MHz, CDCI3): δ = 7.81 (t, aromatic, 4H), 7.55-7.44 (m, aromatic H, 5H), 7.06 (s, aromatic H, 1 H), 6.93 (d, aromatic H, 2H), 4.00 (s, CH3-H, 6H). UVA/is (dichloromethane): 525 nm. Fluorescence (dichloromethane): 635 nm. ε(525) = 42 000 L mol- 1 cm 1.
3-(3-Bromo-4,5-dimethoxyphenyl)-7-(4-bromophenyl)benzo[1 ,2-b:4,5-b']difuran-2,6-dione
Figure imgf000046_0002
The same procedure as described for compound 3e was used except that 4,5-dimethoxy- mandelic acid (1d) and 5-hydroxy-3-phenylbenzofuran-2(3H)-one(4a) were replaced by 3- bromo-4,5-dimethoxy-mandelic acid (1f) and 3-(4-bromophenyl)-5-hydroxybenzofuran- 2(3H)-one (4b). 3f was obtained as a dark brawn solid (60 %). 1H-NMR (300 MHz, CDCI3): δ = 7.70 (d, aromatic, 4H), 7.19 (s, aromatic H, 1 H), 6.87 (d, aromatic H, 2H), 6.61 (d, aromatic H, 1 H), 3.94 (d, CH3-H, 6H). UVA/is (dichloromethane): 441 , 490 nm. Fluorescence (dichloromethane): 645 nm.
Example 3
5-Hydroxy-3-phenylbenzofuran-2(3H)-one (4a).
Figure imgf000047_0001
Hydroquinone (13.8 g, 0.13 mol), DL-mandelic acid (7.6 g, 0.05 mol) were stirred in 30 ml 73 % sulphuric acid at 120 °C for 30 min. After cooling, the mixture was poured carefully into 200 ml ice water. The resulting white solid was filtered off and washed with water until acid free. The product was dried in air, recrystallized from toluene, giving a white powder (10.3 g, 95 %). %). 1 H-NMR (300 MHz, CDCI3): δ = 7.78 (t, aromatic, 3H), 7.15 (d, aromatic, 2H), 7.08 (d, aromatic, 1 H), 6.85 (d, aromatic, 1 H), 6.72 (s, aromatic, 1 H), 4.85 (s, CH-H, 1 H). 3-(4-bromophenyl)-5-hydroxybenz (4b).
Figure imgf000047_0002
Hydroquinone (7.15 g, 65 mmol), 4-bromo-mandelic acid (5 g, 22 mmol) were stirred in 20 ml 73 % sulphuric acid at 120 °C for 30 min. After cooling, the mixture was poured carefully into 100 ml ice water. The resulting white solid was filtered off and washed with water until acid free. The product was dried in air, recrystallized from toluene, giving a white powder (6 g, 90 %). 1 H-NMR (300 MHz, CDCI3): δ = 7.34 (t, aromatic, 2H), 7.25 (d, aromatic, 2H), 7.05 (d, aromatic, 1 H), 6.84 (d, aromatic, 1 H), 6.72 (s, aromatic, 1 H), 4.88 (s, CH-H, 1 H).
Example 4 - Pol
Figure imgf000047_0003
Polymer 21 was made from compound 16 according to the procedure for polymer 20.
Yield: 65%, Molecular weight 1 1 000, Da, PD= 1.6, UV/vis absorption λ =565 nm.
Example 5 - Polymer (5)
Figure imgf000047_0004
9,9-di-n- hexylfluorene-2,7'-bispinakolato-boronester was synthesized according to the literature: Jo, J.; Chi, C; Hoger, S.; Wegner, G.; Yoon, D. Y. Chem. Eur. J. 2004, 10, 2681. The synthesis of polymer 5 was made from 1 equ. of compound 3f and 1 equ. of 9,9-di-n- hexylfluorene-2,7'-bispinakolato-boronester via Suzuki polymerization according to known methods with Pd(PPh3)4 as catalyst and K2CO3 as base in water-toluene mixture. The 1H NMR spectra of polymer 5 is shown in Fig. 1.
Figure imgf000048_0001
2,5-Bis(trimethylstannyl)thiophene was synthesized according to the literature: C. Van Pham, R.S. Macomber, H.B. Mark Jr, H. Zimmer, J. Org. C ?em.1984, 49, 5250.
The synthesis of polymer 6 was made from 1 equ. of compound 3f and 1 equ. of 2,5- Bis(trimethylstannyl)thiophene via Stille polymerization according to known methods with Pd(PPh3)4 as catalyst in toluene. The 1H NMR spectra of polymer 6 is shown in Fig. 2. 3,4-ethylenedioxythien-2-yl trimethylstannane and 3,4-ethylenedithiathien-2-yl trimethyl- stannane where synthesized according to the litterature: C.Wang, J.L. Schindler, C.R. Kan- newurf, M.G. Kanatzidis, Chem. Mater. 1995, 7, 58.
Example 7
3J-Bis(4-(2,3-dihydrothieno[3^-b][1 ^]dioxin-5-yl)phenyl)benzo[1 ,2-b:4,5-b']difuran dione (7a)
Figure imgf000048_0002
In a vial, 200 mg (0.40 mmol) 3,7-bis(4-bromophenyl)benzo[1 ,2-b:4,5-b']difuran-2,6-dione (3b), 305 mg (1.00 mmol) 3,4-ethylenedioxythien-2-yl trimethylstannane and 14 mg (0.012 mmol) tetrakis(triphenylphosphine) palladium(O) were dissolved in 5 ml dry DMF and stirred for 5 min. The mixture was degassed, and heated in the microwave synthesizer at 160 °C for 1 h. After cooling the mixture was diluted with 50 ml DCM, washed with 50 ml brine and 50 ml water. The organic layer was separated, dried over magnesium sulfate and evaporated. The dark product was recrystallized from DCM/methanol. Yield: 196 mg (79 %) 1 H-NMR (400 MHz, CDCI3): δ = 7.87 (d, aromatic, 8H), 6.96 (s, EDOT aromatic H, 2H), 6.41 (s, aromatic, 1 H), 4.33 (t, EDOT-CH2, 8H). UVA/is (dichloromethane): 298, 391 , 590 nm. ε(590) = 63 580 L moM cm 1.
Example 8
3J-Bis(4-(2,3-dihydrothieno[3^-b][1 ,4]dithien-5-yl)phenyl)benzo[1 ,2-b:4,5-b']difuran dione (7b).
Figure imgf000049_0001
The same procedure as described for compound 7a was used except that 3,4- ethylenedioxythien-2-yl trimethylstannane was replaced by 3,4-ethylenedithiathien-2-yl trimethylstannane. A dark solid (200 mg, 89 %) was obtained. 1 H-NMR (400 MHz, CDCI3): δ = 7.85 (d, aromatic, 8H), 6.69 (s, EDTT aromatic H, 2H), 7.09 (s, aromatic, 1 H), 3.24 (t, EDTT-CH2, 8H). UVA/is (dichloromethane): 306, 502 nm. ε(502) = 79 220 L mol 1 cm 1.
Example 9
3,6-Bis(4-bromophenyl)benzo[1 ,2-b:6,5-b']difuran-2,7-dione (8).
Figure imgf000049_0002
Using a Dean Stark apparatus, ortho-qumone (1 .20 g, 10.82 mmol) and 4-bromo-mandelic acid (5.0 g 21.64 mmol) were dissolved in 1 ,2,4-trichlorobenzene (30 ml) and stirred for 5 h at 200°C. After cooling to 60 °C, nitrobenzene (5.0 ml) was added and the mixture was stirred for another hour at 200°C. After cooling to room temperature, 50 ml methanol were added. The solid formed, which was filtered off, washed with methanol and dried in air. 4 was obtained as a dark red solid (3.28 g, 61 %). 1 H-NMR (400 MHz, CDCI3): δ = 7.85 (d, aromatic, 4H), 7.47 (d, aromatic, 4H), 7.16 (d, aromatic, 2H). (m.p. over 300 °C). Anal. Calculated for C22HioBr204: C, 53.05 %; H, 2.02 % . Found : C, 52.10 %; H , 2.90 %. UV/Vis (dichloromethane): λ max at 493 nm.
Example 10
3,6-Bis(4-(2,3-dihydrothieno[3^-b][1 ^^
dione (9a).
Figure imgf000049_0003
The same procedure as described for compound 7a was used but starting from compound 8. A dark solid (93 mg, 82%) was obtained. 1 H-NMR (400 MHz, CDCI3): δ = 7.88 (d, aromatic, 8H), 6.98 (s, EDOT aromatic H, 2H), 7.29 (s, aromatic, 1 H), 4.34 (t, EDOT-CH2, 8H). UVA/is (dichloromethane): 302, 588 nm. ε(588) = 23 080 L moM cm 1.
Example 11
3,6-Bis(4-(2,3-dihydrothieno[3^-b][1 ,4]dithien-5-yl)phenyl)benzo[1 ,2-b:6,5-b']difura dione (9b).
Figure imgf000050_0001
The same procedure as described for compound 7b was followed but starting from compound 8. A dark solid (120 mg, 86%) was obtained. 1H-NMR (400 MHz, CDCI3): δ = 7.84 (d, aromatic, 8H), 7.44 (s, EDTT aromatic H, 2H), 7.09 (s, aromatic, 1 H), 3.27 (t, EDTT- CH2, 8H). UVA/is (dichloromethane): 307, 407, 558 nm. ε(558) = 1 15 560 L moM cm 1.
Example 12
Polymers
The four monomers 7a, 7b, 9a and 9b were homo-electropolymerized by repetitive cycling over the redox active range of the materials. Growth of polymer 10, polymer 11 , polymer 12 and polymer 13 by cyclic voltammetry in dichloromethane using a carbon working electrode, Ag wire pseudo-reference electrode. Supporting electrolyte: 0.1 M TBAPF6. Scan rate: 100 mV s 1; T = 20 °C. The cyclovoltammetric response of the four polymers was studied using films of the polymers on a glassy carbon working electrode in acetonitrile vs. Ag/AgCI.
Polymer (10).
Polymer (
Polymer (
Figure imgf000050_0002
Polymer (13).
Figure imgf000051_0001
Onset of Onset of HOMO-LUMO
UV/nm HOMO/eV LUMO/eV
oxidation/V reduction/V gap/eV
10 589, 745 +0.41 -5.21 0.03 -4.77 0.44
348, 417,
11 +0.50 -5.30 -0.41 -4.39 0.91
752
515, 587,
12 -0.01 -4.79 -0.37 -4.43 0.36
743
13 530, 680 +0.87 -5.67 -0.41 -4.39 1.28
Example 13
Figure imgf000051_0002
Compound 14 was obtained from compound 3b and 3-octyl-thiophene-5-trimethylstannane via Stille coupling reaction according to compound 7a. This compound was then subse
Figure imgf000051_0003
Compound 16 was obtained from compound 8 and 3-octyl-thiophene-5-trimethylstannane via Stille coupling reaction according to compound 7a. This compound was then subsequently brominated with N-bromo-succinimide in chloroforme to get compound 17:
Example 14 - Polymer 18
Figure imgf000052_0001
Compound 15 (200 mg, 0.23 mmol) and thiophene diboronic ester (76 mg, 0.23 mmol), Pd2(dba)3 (6.2 mg, 6.7 mmol), and tri-t-butylphosphine (3 mg, 13. 5 mmol) were dissolved in 20 ml fresh THF. The mixture was degassed and heated to reflux under N2. A solution of potassium carbonate (125 mg, 0.9 mmol) in 2 ml water was added and the reaction mixture was heated for 2 h. After cooling, the reaction mixture was diluted with 50 ml DCM, washed with brine and water. The organic phase was dried, the solvent removed. The product was precipitated in methanol. Yield of polymer 18: 71 %
Molecular weight: 12 000 Da, PD = 1.6, UV/vis absorption: λ =578 nm.
Example 15 -
Figure imgf000052_0002
Polymer 19 was made according to the procedure for polymer 18. Yield of polymer 19: 60%, Molecular weight 10 500, Da, PD= 1.1 , UV/vis absorption λ =562 nm.
Example 16 - Polymer 20
Figure imgf000052_0003
Under N2, FeCI3 (11 1 mg, 0.69 mmol) was dissolved in dry DCM (20 ml). A solution of compound 14 (200 mg, 0.27 mmol) in 5 ml dry DCM was added. The reaction mixture was stirred for a further hour at room temperature. The mixture was diluted with 50 ml DCM and 20 ml 1 M HCI was added. The organic phased was washed twice with brine and water and the dried. The solvent was removed and the crude product was precipitated in methanol and washed with methanol in a soxlett over night.
Yield: 70 %, Molecular weight: 16 000 Da, PD = 1.8, UV/vis absorption: λ ^δδθ nm. According to their broad absorption bands, small band gaps and the reversibility of oxidation and reduction processes, P1 and P2 might be useful for electronic applications.

Claims

Claims
A polymer comprising one or more (repeating) unit(s) of the formula
-Ar- -Ar- -Ar- -Ar: Ar- b 1 -Ar- -Ar- '
(I), wherein Y is a group of formula
Figure imgf000054_0001
a is 1 , 2, or 3, a' is 1 , 2, or 3; b is 0, 1 , 2, or 3; b' is 0, 1 , 2, or 3; c is 0, 1 , C IS 0, 1 , 2, or 3; d is 0, 1 , 2, or 3; d' is 0, 1 , 2, or 3;
U1 is O, S, or NR1;
U2 is O, S, or NR2;
T1 and T2 are independently of each other hydrogen, halogen, hydroxyl, cyano, - COOR103, -OCOR103, -NR11 COR103, -CONR11 R113, -OR103', -SR103', -SOR103', - S02R103', -NR112S02R103', -NR112R113, Ci-C25alkyl, which may be substituted by E and/or interrupted by D, C5-Ci2cycloalkyl, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; C7-C2sarylalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C2oheteroaryl, or C2-C2oheteroaryl which is substituted by G; R1 and R2 may be the same or different and are selected from hydrogen, a Ci- Ciooalkyl group, -COOR103, -COR103, a Ci-Ciooalkyl group which is substituted by one or more halogen atoms, hydroxyl groups, nitro groups, -CN, or C6-Ci8aryl groups and/or interrupted by -O-, -COO-, -OCO-, or -S-; a C7-Ciooarylalkyl group, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; a carbamoyl group, C5-Ci2cycloalkyl, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; a C6-C24aryl group, in particular phenyl or 1- or 2-naphthyl, which can be substituted one to three times with Ci-Cealkyl, Ci-Cethioalkoxy, and/or Ci-Cealkoxy, or pentafluorophenyl,
R103 and R103' are independently of each other Ci-Ciooalkyl, especially C3-C2salkyl, Ci-C25alkyl substituted by E and/or interrupted by D, CF3, C7-C2sarylalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C2oheteroaryl, or C2-C2oheteroaryl which is substituted by G,
Ar2, A and Ar4' have the meaning of Ar1 , or are independently of each
Figure imgf000054_0002
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000056_0002
R3 and R3' are independently of each other hydrogen, halogen, halogenated Ci- C25alkyl, especially CF3, cyano, Ci-C2salkyl, especially C3-C2salkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C7-C2sarylalkyl, or Ci-C25alkoxy;
R104 and R104' are independently of each other hydrogen, cyano, COOR103, or a Ci- C25alkyl group,
R4, R4', R5, R5', R6 and R6' are independently of each other hydrogen, halogen, halogenated Ci-C25alkyl, especially CF3, cyano, Ci-C2salkyl, especially C3-C2salkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms;
C7-C25arylalkyl, or Ci-C2salkoxy;
R114 is Ci-C25alkyl, especially C3-C2salkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms,
R7, R7', R9 and R9' are independently of each other hydrogen, Ci-C2salkyl, especially C3-C25alkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms; or C7-C2sarylalkyl,
R8 and R8' are independently of each other hydrogen, Ce-Ciearyl; Ce-Ciearyl which is substituted by Ci-Ciealkyl, or Ci-Ciealkoxy; or Ci-C2salkyl, especially C3-C2salkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; or C7-C25arylalkyl,
R11 and R11 ' are independently of each other Ci-C2salkyl group, especially a Ci- Cealkyl group, C7-C2sarylalkyl, or a phenyl group, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy;
R12 and R12' are independently of each other hydrogen, halogen, cyano, Ci-C2salkyl, especially C3-C2salkyl, which may optionally be interrupted by one, or more oxygen, or sulphur atoms, Ci-C2salkoxy, C7-C2sarylalkyl, or ^ , wherein R13 is a Ci-
Cioalkyl group, or a tri(Ci-C8alkyl)silyl group;
Figure imgf000057_0001
RIO5i RKW Rio6 and Rio6 are independently of each other hydrogen, halogen, cyano, Ci-C25alkyl, which may optionally be interrupted by one or more oxygen or sulphur atoms; C7-C2sarylalkyl, or Ci-Ciealkoxy,
R107 is hydrogen, C7-C2sarylalkyl, Ce-Ciearyl; Ce-Ciearyl which is substituted by Ci- Ciealkyl, or Ci-Ciealkoxy; Ci-Ci8perfluoroalkyl; Ci-C2salkyl; especially C3-C2salkyl, which may be interrupted by -0-, or -S-; or -COOR103; R103 is is as defined above; R108 and R1°9 are independently of each other H, Ci-C25alkyl, Ci-C25alkyl which is substituted by E and/or interrupted by D, C7-C2sarylalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C2oheteroaryl, C2-C2oheteroaryl which is substituted by G, C2- Ciealkenyl, C2-Ci8alkynyl, Ci-Ciealkoxy, Ci-Ciealkoxy which is substituted by E and/or interrupted by D, or C7-C2saralkyl, or
R108 and R109 together form a group of formula =CR110R111 , wherein
R110 and R111 are independently of each other H, Ci-Ciealkyl, Ci-Ciealkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6-C24aryl which is substituted by G, or C2-C2oheteroaryl, or C2-C2oheteroaryl which is substituted by G, or
R108 and R109 together form a five or six membered ring, which optionally can be substituted by Ci-Ciealkyl, Ci-Ciealkyl which is substituted by E and/or interrupted by D, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C2oheteroaryl, C2- C2oheteroaryl which is substituted by G, C2-Ci8alkenyl, C2-Ci8alkynyl, Ci-Ciealkoxy, Ci-Ciealkoxy which is substituted by E and/or interrupted by D, or C7-C2saralkyl, D is -CO-, -COO-, -S-, -0-, or -NRH2-,
E is Ci-C8thioalkoxy, Ci-C8alkoxy, CN, -NR^Rm, -CONR112R113, or halogen, G is E, or Ci-Ciealkyl, and
R112 and R113 are independently of each other H; C6-Ci8aryl; C6-Ci8aryl which is substituted by Ci-Ciealkyl, or Ci-Ciealkoxy; Ci-Ciealkyl; or Ci-Ciealkyl which is interrupted by -0-. The polymer according to claim 1 , which is a polymer comprising one or more (repeating) unit(s) of the formula
or
Figure imgf000058_0001
U1 is O, S, or NR1;
U2 is O, S, or NR2;
T1 and T2 are independently of each other hydrogen, halogen, hydroxyl, cyano, - COOR103, -OCOR103, -NR11 COR103, -CONR11 R113, -OR103', -SR103', -SOR103', - S02R103', -NR112S02R103', -NR112R113, Ci-C25alkyl, which which may be substituted by E and/or interrupted by D, C5-Ci2cycloalkyl, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; C7-C2sarylalkyl, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C2oheteroaryl, or C2-C2oheteroaryl which is substituted by G;
R1 and R2 may be the same or different and are selected from hydrogen, a Ci- Ciooalkyl group, -COOR103, -COR103, a Ci-Ciooalkyl group which is substituted by one or more halogen atoms, hydroxyl groups, nitro groups, -CN, or C6-Ci8aryl groups and/or interrupted by -O-, -COO-, -OCO-, or -S-; a C7-Ciooarylalkyl group, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; a carbamoyl group, C5-Ci2cycloalkyl, which can be substituted one to three times with Ci-Cealkyl and/or Ci-Cealkoxy; a C6-C24aryl group, in particular phenyl or 1- or 2-naphthyl, which can be substituted one to three times with Ci-Cealkyl, Ci-Cethioalkoxy, and/or Ci-Cealkoxy, or pentafluorophenyl;
a is 1 , 2, or 3, a' is 1 , 2, or 3; wherein Ar1 and Ar1 ' are independently of each other a group of formula (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), or (XVh) (as defined in claim 1); and R103, R103', R112, R113, D, E and G are as defined in claim 1 ; or a polymer comprising on (s) of the formula
-Ar-
Jb -Ar!
Figure imgf000058_0002
(I"), wherein a is 1 , or 2;, a' is 1 , or 2; b is 1 , 2, or 3; b' is 1 , 2, or 3; wherein Y, Ar1 and Ar1 ' are as defined above; and Ar2 and Ar2' are as defined in claim 1.
3. The polymer according to claim 1 , or 2, comprising one or more (repeating) unit(s) of the formula
Figure imgf000059_0001
Figure imgf000060_0001
n
U1 is O, or NR1 ;
U2 is O, or NR2;
T1 and T2 are independently of each other hydrogen, or Ci-C2salkyl, especially hydrogen;
R1 and R2 may be the same or different and are selected from a Ci-C38alkyl group, especially a Ce-C36alkyl group;
RIO5i 105', R106 anc| Rio6 are independently of each other hydrogen or Ci-C2salkyl; and
R107 and R107' are independently of each other hydrogen or Ci-C2salkyl, especially Ci-C25alkyl;
R108 and R109 are independently of each other H, or Ci-C2salkyl. or 2, comprising (repeating) unit(s) of the formula
Figure imgf000060_0002
(II), wherein
A is a repeating unit of formula (I), and
-COM1- is a repeating unit, which has the meaning of Ar2, wherein Ar2 is as defined
14 15 17
-Ar -Ar -Ar- -Ar
in claim 1 , or a group of formula
k is 1 , 1 is 1 , r is 0, or 1 , z is 0, or 1 , and
a group of formula
Figure imgf000060_0003
wherein one of X5 and X6 is N and the other is CR14, and R14, R14', R17 and R17' are independently of each other H, or a Ci-C2salkyl group, especially a C6-C25alkyl, which may optionally be interrupted by one or more oxygen atoms. he polymer according to claim 4, wherein A is a repeating unit of formula (la), (Ic), for-
Figure imgf000061_0001
other hydrogen, or Ci-C25alky, R104 and R104' are independently of each other hydrogen, cyano or a Ci-C2salkyl group, and R14 and R14 are independently of each other H, or a Ci-C25alkyl group, especially a C6-C2salkyl, which may optionally be interrupted by one or more oxygen atoms.
Figure imgf000061_0002
Figure imgf000062_0001
(lid), wherein
n is 4 to 1000, especially 4 to 200, very especially 5 to 100,
T1 and T2 are independently of each other hydrogen, or Ci-C2salkyl, especially hydrogen;
R1 is a Ci-C38alkyl group, especially a Ce-C36alkyl group,
R3 is hydrogen, halogen, cyano, Ci-C2salkyl or Ci-C2salkoxy, especially hydrogen or Ci-C25alkyl;
R105 and R105' are independently of each other hydrogen, halogen, cyano, Ci-C2salkyl or Ci-C25alkoxy, especially hydrogen or Ci-C2salkyl;
R106 and R106' are independently of each other hydrogen or Ci-C2salkyl; and
R108 and R109 are independently of each other H, or Ci-C2salkyl.
7. A compound of the formula
Figure imgf000062_0002
(III), wherein a, a', b, b', c, c', d, d', Y, Ar1, Ar1 ', Ar2, Ar2', Ar3, Ar3', Ar4 and Ar4' are as defined in claim 1 ,
R10 and R10' are independently of each other hydrogen, halogen, cyano, Ci-C2salkyl, Ci-C25alkoxy, C6-C24aryl, C6-C24aryl which is substituted by G, C2-C2oheteroaryl, C2- C2oheteroaryl which is substituted by G, especially a group of one of the formulae
Figure imgf000062_0003
Figure imgf000063_0001
wherein R22 to R26 and R29 to R58 represent independently of each other H , halogen, cyano, Ci-C2salkyl, Ci-C2salkyl which is substituted by E and/or interrupted by D, C6- C24aryl, C6-C24aryl which is substituted by G, C2-C2oheteroaryl, C2-C2oheteroaryl which is substituted by G, a C4-Ci8cycloalkyl group, a C4-Ci8cycloalkyl group, which is substituted by G, C2-Ci8alkenyl, C2-Ci8alkynyl, Ci-Ciealkoxy, Ci-Ciealkoxy which is substituted by E and/or interrupted by D, C7-C2saralkyl, or C7-C2saralkyl, which is substituted by G,
R27 and R28 are independently of each other hydrogen, Ci-C2salkyl, halogen, cyano or C7-C25aralkyl, or R27 and R28 together represent alkylene or alkenylene which may be both bonded via oxygen and/or sulfur to the thienyl residue and which may both have up to 25 carbon atoms,
D is -CO-, -COO-, -S-, -0-, or -N R^2-,
E is Ci-C8thioalkoxy, Ci-C8alkoxy, CN, -N R112 113, -CON RH2RH3, 0r halogen, G is E, or Ci-Ciealkyl, and
R1 12 and R1 13 are independently of each other H ; C6-Ci8aryl; C6-Ci8aryl which is substituted by Ci-Ciealkyl, or Ci-Ciealkoxy; Ci-Ciealkyl; or Ci-Ciealkyl which is interrupted by -0-, with the proviso that Ar1 and Ar1 ' are not a group of formula (XVa), if b, b', c, c', d and d' are 0 and R10 and R10' are independently of each other hydrogen, halogen, Ci-C2salkyl, or Ci-C2salkoxy.
An organic semiconductor material, layer or component, comprising a polymer according to any of claims 1 to 6 and/or a compound according to claim 7.
A semiconductor device, comprising a polymer according to any of claims 1 to 6, a compound according to claim 7 and/or an organic semiconductor material, layer or component according to claim 8.
The semiconductor device according to claim 9, which is an organic photovoltaic (PV) device (solar cell), a photodiode, or an organic field effect transistor.
11. Process for the preparation of an organic semiconductor device, which process comprises applying a solution and/or dispersion of a polymer according to any of claims 1 to 6 and/or a compound according to claim 7 in an organic solvent to a suitable substrate and removing the solvent; or which process comprises evaporation of a compound according to claim 7.
12. Use of the polymer according to any of claims 1 to 6, the compound according to claim 7 and/or the organic semiconductor material, layer or component according to claim 7 in PV devices, photodiodes, or organic field effect transistors.
13. A compound of the formula
Figure imgf000064_0001
wherein a, a', b, b', c, c', d, d', Y, Ar1, Ar1 ', Ar2, Ar2', Ar3, Ar3', Ar4 and Ar4' are as defined in claim 1 , and X is halogen, especially Br, or J, ZnX12, -SnR^R^eF^ wherein R207, R208 and R209 are identical or different and are H or Ci-C6alkyl, wherein two radicals optionally form a common ring and these radicals are optionally branched or unbranched and X12 is a halogen atom, very especially I, or Br; or -
OS(0)2CF3, -OS(0)2-aryl, especially
Figure imgf000064_0002
-OS(0)2CH3, -B(OH)2,
-B(OY1)2,
Figure imgf000064_0003
, -BF4Na, or -BF4K, wherein Y1 is independently in each occurrence a Ci-Cioalkyl group and Y2 is independently in each occurrence a C2-Ci0alkylene group, such as -CY3Y4-CYSY6-, or -CY7Y8-CY9Y1o- CY11Y12-, wherein Y3, Y4, Y¾, Y¾, Y7, γβ, γ9, Y1o, γιι and Y12 are independently of each other hydrogen, or a Ci-Cioalkyl group, especially -C(CH3)2C(CH3)2-,
-C(CH3)2CH2C(CH3)2-, or -CH2C(CH3)2CH2-, and Y« and Y14 are independently of each other hydrogen, or a Ci-Cioalkyl group.
-COM1
I L J L n
14. A process for the preparation of a polymer of formula
comprising reacting a
dihalogenide of formula with an equimolar amount of a diboronic acid
X -COM1 -X
or diboronate corresponding to formula or
X -COM1 -X
reacting a dihalogenide of formula with an equimolar amount of a diboronic acid or diboronate corresponding to formula , wherein X10 is halogen, especially Br, and X11 is independently in each occurrence -B(OH)2, -B(0Y1)2,
Figure imgf000065_0001
, wherein Y1 is independently in each occurrence a Ci-Cioalkyl group and Y2 is independently in each occurrence a C2- Cioalkylene group, such as -CY3Y4-CYSY6-, or -CY7Y8-CY9Y1o- CY11Y12-, wherein Y3, Y4, Y5, Y6, Y , Y8, Y9, γιο, γι ι anc| γΐ23ΓΘ independently of each other hydrogen, or a Ci-Ci0alkyl group, especially -C(CH3)2C(CH3)2-, -C(CH3)2CH2C(CH3)2-, or -CH2C(CH3)2CH2-, and Y13 and Y14 are independently of each other hydrogen, or a Ci-Cioalkyl group, in a solvent and in the presence of a catalyst; or
reacting a dihalogenide of formula with an equimolar amount of an or-
X11- -COM1- -X1 1'
gano tin compound corresponding to formula , or
X10- -COM1- -X10
reacting a dihalogenide of formula with an equimolar amount of an organo tin compound corresponding to formula , wherein
X11' is independently in each occurrence -SnR20 R208 209 wherein R2°7, R208 anc| R209 are identical or different and are H or Ci-C6alkyl, or two of the groups R207, R208 and R209 form a ring and these groups are optionally branched, A and COM1 are as defined in claim 4 and n is in the range of 4 to 1000, especially 4 to 200, very especially 5 to 150.
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US9240551B2 (en) 2011-10-04 2016-01-19 Basf Se Polymers based on benzodiones
CN104781367B (en) * 2012-11-07 2017-04-26 巴斯夫欧洲公司 Polymers based on naphthodiones
CN112851916A (en) * 2021-01-08 2021-05-28 青岛科技大学 Aromatic heterocyclic conjugated polymer based on benzofuranone, preparation method and application thereof, and organic field effect transistor
CN112851916B (en) * 2021-01-08 2022-03-25 青岛科技大学 Aromatic heterocyclic conjugated polymer based on benzofuranone, preparation method and application thereof, and organic field effect transistor

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