WO2012146574A1 - Semiconductor materials based on diketopiperidinopiperidine copolymers - Google Patents
Semiconductor materials based on diketopiperidinopiperidine copolymers Download PDFInfo
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- WO2012146574A1 WO2012146574A1 PCT/EP2012/057438 EP2012057438W WO2012146574A1 WO 2012146574 A1 WO2012146574 A1 WO 2012146574A1 EP 2012057438 W EP2012057438 W EP 2012057438W WO 2012146574 A1 WO2012146574 A1 WO 2012146574A1
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- WIPO (PCT)
- Prior art keywords
- alkyl
- cor
- monovalent
- independently
- substituents
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title description 5
- 229920001577 copolymer Polymers 0.000 title description 2
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- 125000001424 substituent group Chemical group 0.000 claims description 185
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 181
- 229910052736 halogen Inorganic materials 0.000 claims description 83
- 150000002367 halogens Chemical class 0.000 claims description 83
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 73
- 125000002950 monocyclic group Chemical group 0.000 claims description 40
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- 238000006243 chemical reaction Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 10
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
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- YLEIFZAVNWDOBM-ZTNXSLBXSA-N ac1l9hc7 Chemical compound C([C@H]12)C[C@@H](C([C@@H](O)CC3)(C)C)[C@@]43C[C@@]14CC[C@@]1(C)[C@@]2(C)C[C@@H]2O[C@]3(O)[C@H](O)C(C)(C)O[C@@H]3[C@@H](C)[C@H]12 YLEIFZAVNWDOBM-ZTNXSLBXSA-N 0.000 description 3
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- 125000002785 azepinyl group Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
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- 239000002244 precipitate Substances 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 description 1
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- FANCTJAFZSYTIS-IQUVVAJASA-N (1r,3s,5z)-5-[(2e)-2-[(1r,3as,7ar)-7a-methyl-1-[(2r)-4-(phenylsulfonimidoyl)butan-2-yl]-2,3,3a,5,6,7-hexahydro-1h-inden-4-ylidene]ethylidene]-4-methylidenecyclohexane-1,3-diol Chemical compound C([C@@H](C)[C@@H]1[C@]2(CCCC(/[C@@H]2CC1)=C\C=C\1C([C@@H](O)C[C@H](O)C/1)=C)C)CS(=N)(=O)C1=CC=CC=C1 FANCTJAFZSYTIS-IQUVVAJASA-N 0.000 description 1
- SHAHPWSYJFYMRX-GDLCADMTSA-N (2S)-2-(4-{[(1R,2S)-2-hydroxycyclopentyl]methyl}phenyl)propanoic acid Chemical compound C1=CC([C@@H](C(O)=O)C)=CC=C1C[C@@H]1[C@@H](O)CCC1 SHAHPWSYJFYMRX-GDLCADMTSA-N 0.000 description 1
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- 125000004529 1,2,3-triazinyl group Chemical group N1=NN=C(C=C1)* 0.000 description 1
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- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- 238000005481 NMR spectroscopy Methods 0.000 description 1
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- 125000005968 oxazolinyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000005564 oxazolylene group Chemical group 0.000 description 1
- 125000003551 oxepanyl group Chemical group 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000005562 phenanthrylene group Chemical group 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001042 pteridinyl group Chemical group N1=C(N=CC2=NC=CN=C12)* 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000005550 pyrazinylene group Chemical group 0.000 description 1
- 125000003072 pyrazolidinyl group Chemical group 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000005548 pyrenylene group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000005551 pyridylene group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000005576 pyrimidinylene group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 125000003507 tetrahydrothiofenyl group Chemical group 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000005458 thianyl group Chemical group 0.000 description 1
- 125000004305 thiazinyl group Chemical group S1NC(=CC=C1)* 0.000 description 1
- 125000001984 thiazolidinyl group Chemical group 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000005557 thiazolylene group Chemical group 0.000 description 1
- 125000004588 thienopyridyl group Chemical group S1C(=CC2=C1C=CC=N2)* 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000001583 thiepanyl group Chemical group 0.000 description 1
- 125000003777 thiepinyl group Chemical group 0.000 description 1
- ARYHTUPFQTUBBG-UHFFFAOYSA-N thiophen-2-ylboronic acid Chemical compound OB(O)C1=CC=CS1 ARYHTUPFQTUBBG-UHFFFAOYSA-N 0.000 description 1
- 125000005730 thiophenylene group Chemical group 0.000 description 1
- UKTDFYOZPFNQOQ-UHFFFAOYSA-N tributyl(thiophen-2-yl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC=CS1 UKTDFYOZPFNQOQ-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- JQSHBVHOMNKWFT-DTORHVGOSA-N varenicline Chemical compound C12=CC3=NC=CN=C3C=C2[C@H]2C[C@@H]1CNC2 JQSHBVHOMNKWFT-DTORHVGOSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
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- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
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- C09B57/00—Other synthetic dyes of known constitution
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- 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
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- C08G2261/10—Definition of the polymer structure
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- C08G2261/124—Copolymers alternating
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- C08G2261/10—Definition of the polymer structure
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- C08G2261/141—Side-chains having aliphatic units
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- 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
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- 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
- C08G2261/3243—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 sulfur atoms as the only heteroatom, e.g. benzothiophene
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- 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
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
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- C08G2261/90—Applications
- C08G2261/92—TFT applications
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- 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 potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
Definitions
- Organic semiconducting materials can be used in electronic devices such as organic photo- voltaic devices (OPVs), organic field-effect transistors (OFETs), organic light emitting diodes (OLEDs), and organic electrochromic devices (ECDs).
- OCVs organic photo- voltaic devices
- OFETs organic field-effect transistors
- OLEDs organic light emitting diodes
- ECDs organic electrochromic devices
- the organic semiconducting material-based devices show high charge carrier mobility as well as high stability, in particular to- wards oxidation by air, under ambient environmental conditions.
- the organic semiconducting materials are compatible with liquid processing techniques such as spin coating as liquid processing techniques are convenient from the point of processability, and thus allow the production of low cost organic semiconduct- ing material-based electronic devices.
- liquid processing techniques are also compatible with plastic substrates, and thus allow the production of light weight and mechanically flexible organic semiconducting material-based electronic devices.
- Bao, Z.; Dobadalapur, A.; Lovinger, A. J. Appl. Phys. Lett. 1996, 69, 4108-41 10 describes the use of regioregular poly(3-hexylthiophene) in field-effect transistors.
- OFETs organic field effect transistors
- OFETs organic field effect transistors
- Diketopiperidinopiperidine derivatives are also known in the art.
- Ar C 6 H 5 , 2-MeC 6 H 4 , 2,4,6-Me '3,C R 6H' ',2
- the semiconducting material of the present invention is a polymer comprising a unit of formula
- R 1 and R 2 are independently from each other H, Ci-30-alkyl optionally substituted with 1 to 6 substituents R c , C2-3o-alkenyl optionally substituted with 1 to 6 substituents R c , C2-3o-alkynyl optionally substituted with 1 to 6 substituents R c , C3-io-cycloalkyl optionally substituted with 1 to 6 substituents R d , Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents R d , monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents R d , C6-i4-aryl optionally substituted with 1 to 6 substituents R e or monovalent 5 to14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R e , wherein
- G 1 and G 2 are independently from each other -i4-arylene optionally substituted with 1 to 6 substituents R a or bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R a , wherein
- R 8 and R 9 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C 2- 3o-alkenyl, C 2- 3o-alkynyl, -io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
- G 1 and G 2 are independently from each other
- R 5 and R 6 are independently from each other H or Ci
- R 12 and R 13 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C 2- 3o-alkenyl, C 2- 3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
- R 16 and R 17 are independently from each other H , Ci-30-alkyl, -CN or halogen,
- q and s are independently from each other 0, 1 , 2, 3, 4 or 5, r is 0, 1 or 2, and n is an integer from 2 to 10 ⁇ 00.
- the semiconducting material of the present invention is a polymer consisting essentially of a unit of formula wherein R 1 and R 2 are independently from each other H , Ci-30-alkyl optionally substituted with 1 to 6 substituents R c , C2-3o-alkenyl optionally substituted with 1 to 6 substituents R c , C2-3o-alkynyl optionally substituted with 1 to 6 substituents R c , C3-io-cycloalkyl optionally substituted with 1 to 6 substituents R d , Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents R d , monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents R d , C6-i4-aryl optionally substituted with 1 to 6 substituents R e or monovalent 5 to14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R e
- G 1 and G 2 are independently from each other C6-i4-arylene optionally substituted with 1 to 6 substituents R a or bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R a , wherein
- R 10 and R 11 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C 2- io-alkenyl, C 2- io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic hetero- cyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue, or
- G 1 and G 2 are independently from each other
- R 5 and R 6 are independently from each other H or Ci-30-alkyl
- L is C6-24-arylene optionally substituted with 1 to 6 substituents R b or bivalent 5 to 24 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R b , wherein
- R 12 and R 13 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C 2- 3o-alkenyl, C 2- 3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
- R 16 and R 17 are independently from each other H, Ci-30-alkyl, -CN or halogen,
- q and s are independently from each other 0, 1 , 2, 3, 4 or 5, r is 0, 1 or 2, and n is an integer from 2 to 10 ⁇ 00.
- the term "consisting essentially of” means that at least 80% by weight. Preferably at least 90% by weight, of the polymer consists of a unit of formula (1 ) based on the weight of the polymer.
- the semiconducting material of the present invention is a polymer of formula wherein R 1 and R 2 are independently from each other H , Ci-30-alkyl optionally substituted with 1 to 6 substituents R c , C2-3o-alkenyl optionally substituted with 1 to 6 substituents R c , C2-3o-alkynyl optionally substituted with 1 to 6 substituents R c , C3-io-cycloalkyl optionally substituted with 1 to 6 substituents R d , Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents R d , monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents R d , C6-i4-aryl optionally substituted with 1 to 6 substituents R e or monovalent 5 to14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R e , wherein
- G 1 and G 2 are independently from each other -i4-arylene optionally substituted with 1 to 6 substituents R a or bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R a , wherein
- G 1 and G 2 are independently from each other
- R 5 and R 6 are independently from each other H or Ci-30-alkyl
- L is C6-24-arylene optionally substituted with 1 to 6 substituents R b or bivalent 5 to 24 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R b , wherein
- R 12 and R 13 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C 2- 3o-alkenyl, C 2- 3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
- R 16 and R 17 are independently from each other H, Ci-30-alkyl, -CN or halogen,
- q and s are independently from each other 0, 1 , 2, 3, 4 or 5, r is 0, 1 or 2, and n is an integer from 2 to 10 ⁇ 00.
- Ci-12-alkyl, Ci-16-alkyl, C6- 2 o-alkyl and Ci-30-alkyl can be branched or unbranched.
- Examples of Ci-12-alkyl are Ci-10-alkyl and n-undecyl and n-dodecyl.
- Examples of Ci-16-alkyl are Ci-i 2 -alkyl and n-tridecyl, n-tetradecyl, n-pentadecyl and n-hexadecyl.
- Ci-30-alkyl are examples of Ci-12-alkyl, Ci-16-alkyl, C6- 2 o-alkyl and Ci-30-alkyl.
- Ci-io-alkyl and n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-icosyl (C 20 ), n-docosyl (C 22 ), n-tetracosyl (C 24 ), n-hexacosyl (C 2 6) , n-octacosyl (C 2 s) and n-triacontyl (C30).
- C6- 2 o-alkyl examples include n-hexyl, n-heptyl, n-octyl, n-(2-ethyl)hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-icosyl (C20)
- C2-io-alkenyl and C2-3o-alkenyl can be branched or unbranched.
- C2-io-alkenyl examples include vinyl, propenyl, c/s-2-butenyl, frans-2-butenyl, 3-butenyl, c/s-2-pentenyl, frans-2-pentenyl, c/s-3-pentenyl, frans-3-pentenyl, 4-pentenyl, 2-methyl-3-butenyl, hexenyl, heptenyl, octenyl, nonenyl and docenyl.
- C2-3o-alkenyl examples include C2-io-alkenyl, and linoleyl (ds), linolenyl (Cis), oleyl (Cis), arachidonyl (C20), and erucyl (C22).
- C2-io-alkynyl and C2-3o-alkynyl can be branched or unbranched.
- Examples of C2-io-alkynyl are ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl and de- cynyl.
- C2-3o-alkynyl examples include C2-io-alkynyl, and undecynyl, dodecynyl, undecynyl, dode- cynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonade- cynyl and icosynyl (C20).
- C3-io-cycloalkyl are preferably monocyclic C3-io-cycloalkyls such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, but include also polycyclic C3-io-cycloalkyls such as decalinyl, norbornyl and adamantyl.
- Cs-io-cycloalkenyl are preferably monocyclic Cs-io-cycloalkenyls such as cyclopen- tenyl, cyclohexenyl, cyclohexadienyl and cycloheptatrienyl, but include also polycyclic
- Cs-io-cycloalkenyls examples include monovalent 3 to 14 membered aliphatic heterocyclic residues.
- monovalent 3 to 14 membered aliphatic heterocyclic residues are monocyclic monovalent 3 to 8 membered aliphatic cyclic residues and polycyclic, for example bicyclic monovalent 7 to 12 membered aliphatic heterocyclic residues.
- Examples of monocyclic monovalent 3 to 8 membered aliphatic heterocyclic residues are mon- ocyclic monovalent 5 membered aliphatic heterocyclic residues containing one heteroatom such as pyrrolidinyl, 1 -pyrrolinyl, 2-pyrrolinyl, 3-pyrrolinyl, tetrahydrofuryl, 2,3-dihydrofuryl, tetrahy- drothiophenyl and 2,3-dihydrothiophenyl, monocyclic monovalent 5 membered aliphatic heterocyclic residues containing two heteroatoms such as imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, oxazolidinyl, oxazolinyl, isoxazolidinyl, isoxazolinyl, thiazolidinyl, thiazolinyl, isothia- zolidinyl and is
- bicyclic monovalent 7-12 membered aliphatic heterocyclic residue is decahy- dronaphthyl.
- C6-i4-aryl can be monocyclic or polycyclic.
- Examples of C6-i4-aryl are monocyclic C6-aryl such as phenyl, bicyclic Cg-io-aryl such as 1 -naphthyl, 2-naphthyl, indenyl, indanyl and tetrahy- dronaphthyl, and tricyclic Ci2-i4-aryl such as anthryl, phenanthryl, fluorenyl and s-indacenyl.
- the monovalent 5 to 14 membered aromatic heterocyclic residues can be monocyclic monovalent 5 to 8 membered aromatic heterocyclic residues, or polycyclic, for example bicyclic mono- valent 7 to 12 membered, tricyclic monovalent 9 to 14 membered aromatic heterocyclic residue, or tetracyclic monovalent 9 to 14 membered aromatic heterocyclic residues.
- Examples of monocyclic monovalent 5 to 8 membered aromatic heterocyclic residues are mon- ocyclic monovalent 5 membered aromatic heterocyclic residues containing one heteroatom such as pyrrolyl, furyl and thiophenyl, monocyclic monovalent 5 membered aromatic heterocyclic residues containing two heteroatoms such as imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thia- zolyl, isothiazolyl, monocyclic monovalent 5 membered aromatic heterocyclic residues containing three heteroatoms such as 1 ,2,3-triazolyl, 1 ,2,4-triazolyl and oxadiazolyl, monocyclic mono- valent 5 membered aromatic heterocyclic residues containing four heteroatoms such as tetra- zolyl, monocyclic monovalent 6 membered aromatic heterocyclic residues containing one heteroatom such as pyridyl, monocyclic monovalent 6 membered aromatic hetero
- bicyclic monovalent 7 to 12 membered aromatic heterocyclic residues are bicyclic monovalent 8 membered aromatic heterocyclic residues containing two heteroatoms such as thieno[3,2-b]thiophenyl, bicyclic 9 membered aromatic heterocyclic residues containing one heteroatom such as indolyl, isoindolyl, indolizinyl, indolinyl, benzofuryl, isobenzofuryl, ben- zothiophenyl and isobenzothiophenyl, bicyclic monovalent 9 membered aromatic heterocyclic residues containing two heteroatoms such as indazolyl, benzimidazolyl, benzimidazolinyl, ben- zoxazolyl, benzisooxazolyl, benzthiazolyl, benzisothiazolyl, furopyridyl and thienopyridyl, bicyclic monovalent 9 membered aromatic heterocyclic
- tricyclic monovalent 9 to 14 membered aromatic heterocyclic residues examples include dibenzo- furyl, acridinyl, phenoxazinyl, 7H-cyclopenta[1 ,2-b:3,4-b']dithiophenyl and 4H-cyclopenta- [2,1 -b:3,4-b']dithiophenyl.
- An example of a tricyclic monovalent 9 to 14 membered aromatic heterocyclic residue containing three heteroatoms is dithienothiophenyl of formula
- halogen examples are -F, -CI, -Br and -I.
- Ci-10-alkoxy examples are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, fert-butoxy, n-pentoxy, neopentoxy, isopentoxy, hexoxy, n-heptoxy, n-octoxy, n-nonoxy and n-decoxy.
- Ci-30-alkoxy are Ci-10-alkoxy, and n-undecoxy,
- n-dodecoxy n-undecoxy, n-dodecoxy, n-tridecoxy, n-tetradecoxy, n-pentadecoxy, n-hexa- decoxy, n-heptadecoxy, n-octadecoxy, n-nonadecoxy and n-icosoxy (C20), n-docosoxy (C22), n-tetracosoxy (C24), n-hexacosoxy (C26), n-octacosoxy (C28) and n-triacontoxy (C30).
- C2-6-alkylene examples include ethylene, butylene, pentylene, hexylene and 2-methylpentylene.
- C6-i4-arylene examples include monocyclic C6-arylene such as phenylene, bicyclic Cg-io-arylene such as naphthylene, for example
- Ci2-i4-arylene such as anthrylene, for example
- phenanthrylene for example fluorenylene
- C6-24-arylene examples include C6-i4-arylene and pyrenylene, for example
- the bivalent 5 to 14 membered aromatic heterocyclic residues can be monocyclic bivalent 5 to 8 membered aromatic heterocyclic residues, or polycyclic, for example bicyclic bivalent 7 to 14 membered, tricyclic bivalent 9 to 14 membered aromatic heterocyclic residues, or tetracyclic bivalent 9 to 14 membered aromatic heterocyclic residues.
- monocyclic bivalent 5 to 8 membered aromatic heterocyclic residues are monocyclic bivalent 5 membered aromatic heterocyclic residues containing one heteroatom such as pyr- rolylene, furylene and thiophenylene, monocyclic bivalent 5 membered aromatic heterocyclic residues containing two heteroatoms such as imidazolylene, pyrazolylene, oxazolylene, isoxa- zolylene, thiazolylene, isothiazolylene, monocyclic bivalent 5 membered aromatic heterocyclic residues containing three heteroatoms such as 1 ,2,3-triazolylene, 1 ,2,4-triazolylene and oxadia- zolylene, monocyclic bivalent 5 membered aromatic heterocyclic residues containing four heteroatoms such as tetrazolylene, monocyclic bivalent 6 membered aromatic heterocyclic residues containing one heteroatom such as pyridylene, monocyclic bivalent 6 membered aromatic heterocyclic residues
- bicyclic bivalent 7 to 14 membered aromatic heterocyclic residues are examples of bicyclic bivalent 7 to 14 membered aromatic heterocyclic residues.
- bicyclic bivalent 8 membered aromatic heterocyclic residues containing three heteroatoms such as as thienothiazolylene for example bicyclic bivalent 8 membered aromatic heterocyclic residues containing four heteroatoms such as thiazothiazolylene, for example bicyclic bivalent 9 membered aromatic heterocyclic residues containing one heteroatom such as indolylene, isoindolylene, indolizinylene, indolinylene, isoindolinylene, for example
- bicyclic bivalent 9 membered aromatic heterocyclic residues containing four heteroatoms such as purinylene
- bicyclic bivalent 10 membered aromatic heterocyclic residues containing one heteroatom such as quinolylene, isoquinolylene, chromenylene and chromanylene
- bicyclic bivalent 10 membered aromatic heterocyclic residues containing two heteroatoms such as quinoxalinylene
- quinazolinylene cinnolinylene, phthalazinylene, 1 ,5-naphthyridinylene and
- bicyclic bivalent 10 membered aromatic heterocyclic residues containing three heteroatoms such as pyridopyrazinylene, pyridopyrimidinylene and pyridopyridazinylene
- bicyclic bivalent 10 membered aromatic heterocyclic residues containing four heteroatoms such as pterid- inylene.
- tricyclic bivalent 9 to 14 membered aromatic heterocyclic residues containing one heteroatom are dibenzofurylene, acridinylene, dibenzosilacyclopentadienylene, for example
- Examples of a tricyclic bivalent 9 to 14 membered aromatic heterocyclic residues containing two heteroatoms are phenoxazinylene, and the following compounds
- tricyclic bivalent 9 to 14 membered aromatic heterocyclic residue containing three heteroatoms are the following compounds
- tricyclic bivalent 9 to 14 membered aromatic heterocyclic residue containing four- heteroatoms are the following compounds
- bivalent 5 to 24 membered aromatic heterocyclic residues are bivalent 5 to 14 membered aromatic heterocyclic residues, and the following compounds
- Examples of L are:
- G 1 and G 2 are independently from each other -i4-arylene optionally substituted with 1 to 6 substituents R a or bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R a , wherein
- R 8 and R 9 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C 2- 3o-alkenyl, C 2- 3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
- G 1 and G 2 are independently from each other
- R 5 and R 6 are independently from each other H or Ci
- L is C6-24-arylene optionally substituted with 1 to 6 substituents R b or bivalent 5 to 24 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R b , wherein
- R 12 and R 13 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue
- R 16 and R 17 are independently from each other H, Ci-30-alkyl, -CN or halogen,
- q and s are independently from each other 0, 1 , 2, 3, 4 or 5, r is 0, 1 or 2, and n is an integer from 2 to 10 ⁇ 00.
- r is 0, 1 or 2
- n is an integer from 2 to 10 ⁇ 00.
- R 1 and R 2 are independently from each other Ci-30-alkyl optionally substituted with 1 to 6 substituents R c , preferably Ci -alkyl optionally substituted with 1 to 6 substituents R c , more preferably Ci-12-alkyl optionally substituted with 1 to 6 substituents R c , wherein
- G 1 and G 2 are independently from each other -i4-arylene optionally substituted with 1 to 6 substituents R a or bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R a , wherein
- R 8 and R 9 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C 2- 3o-alkenyl, C 2- 3o-alkynyl, -io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue
- G 1 and G 2 are independently from each other
- R 5 and R 6 are independently from each other H or Ci-30-alkyl
- L is C6- 2 4-arylene optionally substituted with 1 to 6 substituents R b or bivalent 5 to 24 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R b , wherein
- R 12 and R 13 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
- R 16 and R 17 are independently from each other H, Ci-30-alkyl, -CN or halogen, q and s are independently from each other 0, 1 , 2, 3, 4 or 5, r is 0, 1 or 2, and n is an integer from 2 to 10 ⁇ 00.
- R 1 and R 2 are independently from each other Ci-30-alkyl optionally substituted with 1 to 6 sub- stituents R c , preferably Ci-16-alkyl optionally substituted with 1 to 6 substituents R c , more preferably Ci-12-alkyl optionally substituted with 1 to 6 substituents R c , wherein
- G 1 and G 2 are independently from each other bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R a , wherein
- R 8 and R 9 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cyclo- alkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue
- G 1 and G 2 are independently from each other
- R 5 and R 6 are independently from each other H or Ci-30-alkyl, L is bivalent 5 to 24 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R b , wherein
- R 12 and R 13 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C 2- 3o-alkenyl, C 2- 3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
- R 16 and R 17 are independently from each other H, Ci-30-alkyl, -CN or halogen,
- q and s are independently from each other 0, 1 , 2, 3, 4 or 5, r is 0, 1 or 2, and n is an integer from 2 to 10 ⁇ 00.
- R 1 and R 2 are independently from each other Ci-16-alkyl, more preferably Ci-12-alkyl,
- G 1 and G 2 are independently from each other monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue optionally substituted with 1 to 4 substituents R a , wherein
- R a at each occurrence are independently from each other Ci-30-alkyl optionally substituted with 1 to 4 substituents R f , wherein
- L is bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 4 substituents R b , wherein
- R b at each occurrence are independently from each other Ci-30-alkyl optionally substituted with 1 to 4 substituents R h , wherein
- q and s are independently from each other 1 , 2 or 3, r is 1 or 2, and n is an integer from 5 to 10 ⁇ 00.
- R 1 and R 2 are independently from each other Ci-16-alkyl, more preferably Ci-i 2 -alkyl, G 1 and G 2 are independently from each other monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue, wherein G 1 and G 2 are substituted with 1 to 2 substituents R a , wherein
- R a at each occurrence are independently from each other C6- 2 o-alkyl
- L is bivalent 5 to 14 membered aromatic heterocyclic residue, wherein L is substituted with 1 to 2 substituents R b , wherein
- R b at each occurrence are independently from each other C6- 2 o-alkyl, q and s are both 1 , r is 1 , and n is an integer from 5 to 10 ⁇ 00.
- Particular preferred units of formula (1 ) are units of formula
- R 1 , R 2 , R a , L and n are as defined above.
- R b is as defined above.
- n is an integer from 5 to 5 ⁇ 00, more preferably from 5 to 1 ⁇ 00, even more preferably from 5 to 100, and most preferably from 10 to 100.
- a particular preferred example of the units of formulae (1 ) and (1a) is the unit of formula
- the semiconducting material of the present invention can be a polymer comprising preferably at least 80% by weight, more preferably at least 90% by weight, of a unit of formula (1 ), respectively, (1a) based on the weight of the polymer.
- the semiconducting material of the present invention is a polymer consisting essentially of a unit of formula (1 ), respectively, (1a).
- the polymer comprising a unit of formula (1 ) can be prepared by treating a compound of formula
- R 1 , R 2 , G 1 , G 2 , q and s are as defined above, and Hal 1 is halogen, preferably -Br, with a compound of formula
- L and q are as defined above, and R 100 , R 101 and R 102 are independently from each other Ci-io-alkyl, preferably methyl. in the presence of transition metal catalyst 1 .
- Transition metal catalyst 1 is preferably a palladium catalyst such tris(dibenzylideneacetone)- dipalladium(O), preferably in combination with a phosphine such as tri-otolylphosphine.
- the reaction is preferably performed at elevated temperatures such 80 to 200 °C, preferably 90 to 150 °C.
- the reaction can be performed in an inert organic solvent such as chlorobenzene.
- the reaction can be stopped by the addition of end cappers such as 2-bromothiophene and 2-thiophene boronic acid.
- the crude product may be worked up by conventional methods, for example by extracting the crude product with an appropriate solvent, for example with acetone.
- the compound of formula (2) can be prepared by treating a compound of formula
- R 1 , R 2 , G 1 , G 2 , q and s are as defined above, with a halogenating agent.
- the halogenating agent is preferably /V-bromosuccinimide.
- the reaction is preferably performed at ambient temperatures such -5 to 50 °C, preferably 0 to 30 °C.
- the reaction can be performed in an organic solvent such chloroform.
- the crude product may be worked up by conventional methods, for example by column chromatography.
- the compound of formula (4) can be prepared by reacting a compound of formula
- G 1 , G 2 , q and s are as defined above, and R 200 , R 201 and R 202 are independently from each other Ci-10-alkyl, preferably methyl in the presence of a transition metal catalyst 2.
- Transition metal catalyst 2 is preferably a palladium catalyst such tetrakis(triphenylphosphine) palladium(O).
- the reaction is preferably performed at elevated temperatures such 80 to 200 °C, preferably 90 to 150 °C.
- the reaction can be performed in an inert organic solvent such as di- methylformamide.
- the crude product may be worked up by conventional methods, for example by column chromatography.
- the compound of formula (5) can be prepared by treating a compound of formula
- R 1 and R 2 are as defined above, with a halogenating agent.
- the halogenating agent is preferably Br2.
- the reaction is preferably performed at ambient temperatures such -5 to 30 °C, preferably 0 to 30 °C.
- the reaction can be performed in an organic solvent such dichloromethane.
- the crude product may be worked up by conventional methods.
- the compound of formula (8) can be prepared according to following reaction scheme:
- an electronic device comprising the polymer comprising a unit of formula (1 ) as semiconducting material.
- the electronic device is an organic field effect transistor (OFET), and in particular a thin film transistor (TFT).
- the elec- tronic device is an organic photovoltaic device (OPV).
- an organic field effect transistor comprises a dielectric layer, a semiconducting layer and a substrate.
- organic field effect transistor usually comprises a gate electrode and source/drain electrodes.
- An organic field effect transistor can have various designs.
- BGTC Bottom-Gate Top-Contact
- the semiconducting layer comprises the semiconducting material of the present invention.
- the semiconducting layer can have a thickness of 5 to 500 nm, preferably of 10 to 100 nm, more preferably of 20 to 50 nm.
- the dielectric layer comprises a dielectric material.
- the dielectric material can be silici- um/silicium dioxide, or, preferably, an organic polymer such as polystyrene (PS), polymethylmethacrylate) (PMMA), poly(4-vinylphenol) (PVP), polyvinyl alcohol) (PVA), anzocyclobutene (BCB), or polyimide (PI).
- PS polystyrene
- PMMA polymethylmethacrylate
- PVP poly(4-vinylphenol)
- PVA polyvinyl alcohol
- BCB anzocyclobutene
- PI polyimide
- the dielectric layer can have a thickness of 10 to 2000 nm, preferably of 50 to 1000 nm, more preferably of 100 to 800 nm.
- the source/drain contacts and the gate contact can be made from any suitable material, for example Au.
- the substrate can be any suitable substrate such as glass, or a plastic substrate.
- the substrate is a plastic substrate such as polyethersulfone, polycarbonate, polysulfone, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). More preferably, the plastic substrate is a plastic foil.
- the organic field effect transistor can be prepared by methods known in the art.
- a top-gate bottom-contact (TGBC) thin film transistors can be prepared as follows: first: the source/drain contacts are placed on the substrate, for example by thermal evaporation of the source/drain material; second: the substrate is coated with the semiconduct- ing layer, for example by spin-coating a solution of the semiconducting material in a suitable solvent and drying the semiconducting layer at elevated temperatures, for example at 80 to 100 °C; third: the semiconducting layer is coated with a solution of the dielectric material in a suitable solvent, for example by spin-coating a solution of the dielectric material and drying the dielectric layer at elevated temperatures, for example at 80 to 100 °C; fourth: the gate contact is placed on top of the dielectric layer, for example by thermal evaporation of the gate material.
- TGBC top-gate bottom-contact
- Also part of the present invention is the use of the polymer comprising the unit of formula (1 ) as semiconducting material.
- Electronic devices comprising the semiconducting materials of the present invention show high charge carrier mobility as well as high stability, in particular towards oxidation by air, under ambient environmental conditions.
- the semiconducting materials of the present invention are compatible with liquid processing techniques such as spin coating and thus allow the production of low cost, light weight and flexible electronic devices.
- Methyl iodide (10.9 g, 76.8 mmol) is added to a solution of 1 ,5-naphthyridine (12) (5 g, 38.4 mmol) in MeOH (30 mL) and the reaction mixture is heated at 40 °C over 3 days under N2. The precipitate is filtered and dried under high vacuum to afford compound 1 1a as yellowish green solid (8.51 g, 81 .1 %).
- 1 H NMR 400 MHz, CDCI 3 , r.t) ⁇ 9.49 (d, 1 H), 9.38 (dd, 1 H), 9.26 (d, 1 H), 8.98 (dd, 1 H), 4.75 (s, 3H).
- Pd(PPh 3 )4 (0.1 1 g, 0.10 mmol) is added to a solution of compound 5a (0.68 g, 1.97 mmol) and compounds 6a (2.45 g, 5.90 mmol) in degassed dimethylformamide (23 ml_).
- the reaction mixture is heated to 130 °C and stirred overnight.
- the reaction mixture is allowed to cool to RT, washed with H2O (25 ml_), extracted with CH2CI2 (25 ml. x 3), dried over Na2S0 4 and concentrated.
- the residue is purified by flash column (0 ⁇ 100% ethyl acetate/hexane) to afford com- pound 4a as red solid (0.42 g, 31 %).
- top-gate bottom-contact transistors containing the polymer P1 , essentially consisting of the units of formula 1 b, as semiconducting material
- a top-gate bottom-contact (TGBC) thin film transistor TFT is fabricated on glass (PGO glass used as received).
- Au source-drain contacts (30 nm-thick) are thermally-evaporated.
- the substrate is then coated with the semiconductor layer (thickness: 40 to 50 nm) by spin-coating (1000 rpm) a solution of polymer P1 (prepared as described in example 1 ) in dichloromethane (concentration ⁇ 10 mg/mL), and drying the film at 90 °C for 30 seconds.
- a 4 weight% polysty- rene solution in isopropyl acetate is spin-coated (3600 rpm) and the dielectric film formed is dried at 90 °C for 30 seconds to yield a dielectric layer (thickness: 500 to 600 nm).
- the top-gate, bottom-contact (TGBC) thin film transistors of example 2 show the following mobility: 4 x 10- 3 cm 2 V- 1 s- 1 .
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Abstract
The present invention provides a polymer comprising a unit of formula (1) and an electronic device comprising the polymer as semiconducting material.
Description
Semiconductor materials based on diketopiperidinopiperidine copolymers Description
Organic semiconducting materials can be used in electronic devices such as organic photo- voltaic devices (OPVs), organic field-effect transistors (OFETs), organic light emitting diodes (OLEDs), and organic electrochromic devices (ECDs).
For efficient and long lasting performance, it is desirable that the organic semiconducting material-based devices show high charge carrier mobility as well as high stability, in particular to- wards oxidation by air, under ambient environmental conditions.
Furthermore, it is desirable that the organic semiconducting materials are compatible with liquid processing techniques such as spin coating as liquid processing techniques are convenient from the point of processability, and thus allow the production of low cost organic semiconduct- ing material-based electronic devices. In addition, liquid processing techniques are also compatible with plastic substrates, and thus allow the production of light weight and mechanically flexible organic semiconducting material-based electronic devices.
The use of organic semiconducting materials is known in the art.
Bao, Z.; Dobadalapur, A.; Lovinger, A. J. Appl. Phys. Lett. 1996, 69, 4108-41 10 describes the use of regioregular poly(3-hexylthiophene) in field-effect transistors.
Ong, B. S.; Wu,Y.; Liu, P.; Gardner, S. J. Am. Chem. Soc. 2004, 126, 3378-3379 describes polymers of formula
Zhang, M.; Tsao, H. N.; Pisula, W.; Yang, C; Mishra, A. K.; Mullen, K. J. Am. Chem. Soc. 2007, 129, 3472-3473 describes polymers of formula
L. Burgi, M. Turbiez, R. Pfeiffer, F. Bienewald, H.-J. Kirner, C. Winnewisser, Adv. Mater. 2008, 20, 2217-2224 describes polymers of formula
J. C. Bijleveld, A. P. Zoombelt, S. G. J. Mathijssen, M. M. Wienk, M. Turbiez, D. M. de Leeuw, R. A. J. Janssen, J. Am. Chem. Soc. 2009, 131 , 16616-16617 describes polymers of formula
Diketopiperidinopiperidine derivatives are also known in the art.
E. Bisagni, C. Landras, S. Thirot, C. Huel. Tetrahedron, 1996, 52 (31 ), 10427-10440 describes the synthesis of compound of formula
H. Irikawa, N. Adachi Heterocycles 2000, 53 (1 ), 135-142 describes the synthesis of compound of formula
X = NMe, O
Ar = C6H5, 2-MeC6H4, 2,4,6-Me '3,CR6H' ',2
It was the object of the present invention to provide new organic semiconducting materials. This object is solved by the polymer of claim 1 and the electronic device of claim 17.
The semiconducting material of the present invention is a polymer comprising a unit of formula
R1 and R2 are independently from each other H, Ci-30-alkyl optionally substituted with 1 to 6 substituents Rc, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rc, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rc, C3-io-cycloalkyl optionally substituted with 1 to 6 substituents Rd, Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents Rd, monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents Rd, C6-i4-aryl optionally substituted with 1 to 6 substituents Re or monovalent 5 to14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Re, wherein
Rc at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20- Ci-io-alkyl, -O-COR3, -S-Ci-10-alkyl, -NH2, -NHR3, -NR3R4, -NH-COR3, -COOH, -COOR3, - CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; Rd at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -NO2, -OH, Ci-10-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -O-COR3, -S-Ci-10-alkyl, -NH2, -NHR3, -NR3R4, -NH-COR3, -COOH, -COOR3, -CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, Ci-10-alkyl, C2-io-alkenyl,
C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
Re at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -NO2, -OH, Ci-10-alkoxy, -O-CH2CH2O- Ci-10-alkyl, -O-COR3, -S-Ci-10-alkyl, -NH2, -NHR3, -NR3R4, -NH-COR3, -COOH, -COOR3, - CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-10- cycloalkyl, Cs-io-cycloalkenyl and monovalent 3 to 14 membered aliphatic heterocyclic residue,
wherein R3 and R4 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, -io-cycloalkyl, Cs-io-cyclo- alkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue,
G1 and G2 are independently from each other -i4-arylene optionally substituted with 1 to 6 substituents Ra or bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Ra, wherein
Ra at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-30-alkoxy,
-0-CH2CH20-Ci-3o-alkyl, -O-COR8, -S-Ci-3o-alkyl, -NH2, -NHR8, -NR8R9, -NH-COR8, -COOH, -COOR8, -CONH2, -CONHR8, -CONR8R9, -CO-H, -COR8, Ci-so-alkyl optionally substituted with 1 to 6 substituents Rf, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rf, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rf, -io-cycloalkyl optionally substituted with 1 to 6 substituents Rs, Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents Rs and monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents Rs, wherein
R8 and R9 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, -io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
Rf at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR 0R11, -NH-COR10 -COOH, -COOR10, -CONH2, -CONHR10, -CONR 0R11, -CO-H, -COR10, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
Ra at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR 0R11, -NH-COR10 -COOH, -COOR10, -CONH2, -CONHR10, -CONR 0R11, -CO-H, -COR10, Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, -i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R10 and R11 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl,
C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, Ce-14-aryl and monovalent 5 to14 membered aromatic heterocyclic residue, or
G1 and G2 are independently from each other
R5 and R6 are independently from each other H or Ci
is C6-24-arylene optionally substituted with 1 to 6 substituents Rb or bivalent 5 to 24 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Rb, wherein
Rb at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-30-alkoxy,
-0-CH2CH20-Ci-3o-alkyl, -O-COR12, -S-Ci-3o-alkyl, -NH2, -NHR12, -NR12R13, -NH-COR12, -COOH, -COOR12, -CONH2, -CONHR 2, -CONR 2R13, -CO-H, -COR12, Ci-so-alkyl optionally substituted with 1 to 6 substituents Rh, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rh, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rh, C3-io-cyclo- alkyl optionally substituted with 1 to 6 substituents R', Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents R' and monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents R', wherein
R12 and R13 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
Rh at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-e-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR14, -CONR R15, -CO-H, -COR14, C3-io-cycloalkyl,
monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
R' at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN , -N02, -OH , Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR14, -S-Ci-10-alkyl, -N H2, -N H R14, -N R14R15, -N H-COR14, -COOH , -COOR14, -CON H2, -CON H R 4, -CON R R15, -CO-H , -COR14, Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R14 and R15 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue, or
L is
R16 and R17 are independently from each other H , Ci-30-alkyl, -CN or halogen,
q and s are independently from each other 0, 1 , 2, 3, 4 or 5, r is 0, 1 or 2, and n is an integer from 2 to 10Ό00.
Preferably, the semiconducting material of the present invention is a polymer consisting essentially of a unit of formula
wherein R1 and R2 are independently from each other H , Ci-30-alkyl optionally substituted with 1 to 6 substituents Rc, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rc, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rc, C3-io-cycloalkyl optionally substituted with 1 to 6 substituents Rd, Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents Rd, monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents Rd, C6-i4-aryl optionally substituted with 1 to 6 substituents Re or monovalent 5 to14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Re, wherein
Rc at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN , -N02, -OH , Ci-10-alkoxy, -0-CH2CH20- Ci-io-alkyl, -O-COR3, -S-Ci-10-alkyl, -N H2, -N H R3, -N R3R4, -N H-COR3, -COOH , -COOR3, - CON H2, -CON H R3, -CON R3R4, -CO-H , -COR3, C3-io-cycloalkyl, monovalent 3 to 14 mem- bered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
Rd at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN , -NO2, -OH , Ci-10-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -O-COR3, -S-Ci-10-alkyl, -N H2, -N H R3, -N R3R4, -N H-COR3, -COOH , -COOR3, -CON H2, -CON H R3, -CON R3R4, -CO-H , -COR3, Ci-10-alkyl, C2-io-alkenyl,
C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
Re at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN , -NO2, -OH , Ci-10-alkoxy, -O-CH2CH2O- Ci-10-alkyl, -O-COR3, -S-Ci-10-alkyl, -N H2, -N H R3, -N R3R4, -N H-COR3, -COOH , -COOR3, - CON H2, -CON H R3, -CON R3R4, -CO-H , -COR3, Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-10- cycloalkyl, Cs-io-cycloalkenyl and monovalent 3 to 14 membered aliphatic heterocyclic residue, wherein R3 and R4 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cyclo-
alkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue,
G1 and G2 are independently from each other C6-i4-arylene optionally substituted with 1 to 6 substituents Ra or bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Ra, wherein
Ra at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-30-alkoxy,
-0-CH2CH20-Ci-3o-alkyl, -O-COR8, -S-Ci-3o-alkyl, -NH2, -NHR8, -NR8R9, -NH-COR8, -COOH, -COOR8, -CONH2, -CONHR8, -CONR8R9, -CO-H, -COR8, Ci-so-alkyl optionally substituted with 1 to 6 substituents Rf, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rf, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rf, C3-io-cycloalkyl optionally substituted with 1 to 6 substituents Rs, Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents Rs and monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents Rs, wherein
R8 and R9 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue, Rf at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR 0R11 , -NH-COR10, -COOH, -COOR10, -CONH2, -CONHR10, -CONR 0R11 , -CO-H, -COR10, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monova- lent 5 to 14 membered aromatic heterocyclic residue;
Ra at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR 0R11 , -NH-COR10, -COOH, -COOR10, -CONH2, -CONHR10, -CONR 0R11 , -CO-H, -COR10, Ci-10-alkyl,
C2-io-alkenyl, C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R10 and R11 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic hetero-
cyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue, or
G1 and G2 are independently from each other
R5 and R6 are independently from each other H or Ci-30-alkyl,
L is C6-24-arylene optionally substituted with 1 to 6 substituents Rb or bivalent 5 to 24 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Rb, wherein
Rb at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-30-alkoxy,
-0-CH2CH20-Ci-3o-alkyl, -O-COR12, -S-Ci-3o-alkyl, -NH2, -NHR12, -NR12R13, -NH-COR12,
-COOH, -COOR12, -CONH2, -CONHR 2, -CONR 2R13, -CO-H, -COR12, Ci-so-alkyl optionally substituted with 1 to 6 substituents Rh, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rh, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rh, C3-io-cyclo- alkyl optionally substituted with 1 to 6 substituents R', Cs-io-cycloalkenyl optionally substi- tuted with 1 to 6 substituents R' and monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents R', wherein
R12 and R13 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
Rh at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR14, -CONR R15, -CO-H, -COR14, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
R' at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR14R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR 4, -CONR R15, -CO-H, -COR14, Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R14 and R15 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
R16 and R17 are independently from each other H, Ci-30-alkyl, -CN or halogen,
q and s are independently from each other 0, 1 , 2, 3, 4 or 5, r is 0, 1 or 2, and n is an integer from 2 to 10Ό00.
The term "consisting essentially of" means that at least 80% by weight. Preferably at least 90% by weight, of the polymer consists of a unit of formula (1 ) based on the weight of the polymer.
More preferably, the semiconducting material of the present invention is a polymer of formula
wherein R1 and R2 are independently from each other H , Ci-30-alkyl optionally substituted with 1 to 6 substituents Rc, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rc, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rc, C3-io-cycloalkyl optionally substituted with 1 to 6 substituents Rd, Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents Rd, monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents Rd, C6-i4-aryl optionally substituted with 1 to 6 substituents Re or monovalent 5 to14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Re, wherein
Rc at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN , -N02, -OH , Ci-10-alkoxy, -0-CH2CH20- Ci-io-alkyl, -O-COR3, -S-Ci-10-alkyl, -N H2, -N H R3, -N R3R4, -N H-COR3, -COOH , -COOR3, - CON H2, -CON H R3, -CON R3R4, -CO-H , -COR3, C3-io-cycloalkyl, monovalent 3 to 14 mem- bered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
Rd at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN , -NO2, -OH , Ci-10-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -O-COR3, -S-Ci-10-alkyl, -N H2, -N H R3, -N R3R4, -N H-COR3, -COOH , -COOR3, -CON H2, -CON H R3, -CON R3R4, -CO-H , -COR3, Ci-10-alkyl, C2-io-alkenyl,
C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
Re at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN , -NO2, -OH , Ci-10-alkoxy, -O-CH2CH2O- Ci-10-alkyl, -O-COR3, -S-Ci-10-alkyl, -N H2, -N H R3, -N R3R4, -N H-COR3, -COOH , -COOR3, - CON H2, -CON H R3, -CON R3R4, -CO-H , -COR3, Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-10- cycloalkyl, Cs-io-cycloalkenyl and monovalent 3 to 14 membered aliphatic heterocyclic residue, wherein R3 and R4 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cyclo-
alkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue,
G1 and G2 are independently from each other -i4-arylene optionally substituted with 1 to 6 substituents Ra or bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Ra, wherein
Ra at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-30-alkoxy,
-0-CH2CH20-Ci-3o-alkyl, -O-COR8, -S-Ci-3o-alkyl, -NH2, -NHR8, -NR8R9, -NH-COR8, -COOH, -COOR8, -CONH2, -CONHR8, -CONR8R9, -CO-H, -COR8, Ci-so-alkyl optionally substituted with 1 to 6 substituents Rf, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rf, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rf, C3-io-cycloalkyl optionally substituted with 1 to 6 substituents Rs, Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents Rs and monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents Rs, wherein
R8 and R9 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue, Rf at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR 0R11, -NH-COR10, -COOH, -COOR10, -CONH2, -CONHR10, -CONR 0R11, -CO-H, -COR10, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monova- lent 5 to 14 membered aromatic heterocyclic residue;
Ra at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR 0R11, -NH-COR10, -COOH, -COOR10, -CONH2, -CONHR10, -CONR 0R11, -CO-H, -COR10, Ci-10-alkyl,
C2-io-alkenyl, C2-io-alkynyl, -i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R10 and R11 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic hetero-
cyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue, or
G1 and G2 are independently from each other
R5 and R6 are independently from each other H or Ci-30-alkyl,
L is C6-24-arylene optionally substituted with 1 to 6 substituents Rb or bivalent 5 to 24 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Rb, wherein
Rb at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-30-alkoxy,
-0-CH2CH20-Ci-3o-alkyl, -O-COR12, -S-Ci-3o-alkyl, -NH2, -NHR12, -NR12R13, -NH-COR12,
-COOH, -COOR12, -CONH2, -CONHR 2, -CONR 2R13, -CO-H, -COR12, Ci-so-alkyl optionally substituted with 1 to 6 substituents Rh, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rh, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rh, C3-io-cyclo- alkyl optionally substituted with 1 to 6 substituents R', Cs-io-cycloalkenyl optionally substi- tuted with 1 to 6 substituents R' and monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents R', wherein
R12 and R13 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
Rh at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR14, -CONR R15, -CO-H, -COR14, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
R' at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR14R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR 4, -CONR R15, -CO-H, -COR14, Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R14 and R15 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
R16 and R17 are independently from each other H, Ci-30-alkyl, -CN or halogen,
q and s are independently from each other 0, 1 , 2, 3, 4 or 5, r is 0, 1 or 2, and n is an integer from 2 to 10Ό00.
Ci-12-alkyl, Ci-16-alkyl, C6-2o-alkyl and Ci-30-alkyl can be branched or unbranched. Examples of Ci-12-alkyl are Ci-10-alkyl and n-undecyl and n-dodecyl. Examples of Ci-16-alkyl are Ci-i2-alkyl and n-tridecyl, n-tetradecyl, n-pentadecyl and n-hexadecyl. Examples of Ci-30-alkyl are
Ci-io-alkyl, and n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-icosyl (C20), n-docosyl (C22), n-tetracosyl (C24), n-hexacosyl (C26) , n-octacosyl (C2s) and n-triacontyl (C30). Examples of C6-2o-alkyl are n-hexyl,
n-heptyl, n-octyl, n-(2-ethyl)hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-icosyl (C20) C2-io-alkenyl and C2-3o-alkenyl can be branched or unbranched. Examples of C2-io-alkenyl are vinyl, propenyl, c/s-2-butenyl, frans-2-butenyl, 3-butenyl, c/s-2-pentenyl, frans-2-pentenyl, c/s-3-pentenyl, frans-3-pentenyl, 4-pentenyl, 2-methyl-3-butenyl, hexenyl, heptenyl, octenyl, nonenyl and docenyl. Examples of C2-3o-alkenyl are C2-io-alkenyl, and linoleyl (ds), linolenyl (Cis), oleyl (Cis), arachidonyl (C20), and erucyl (C22).
C2-io-alkynyl and C2-3o-alkynyl can be branched or unbranched. Examples of C2-io-alkynyl are ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl and de- cynyl. Examples of C2-3o-alkynyl are C2-io-alkynyl, and undecynyl, dodecynyl, undecynyl, dode- cynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonade- cynyl and icosynyl (C20).
Examples of C3-io-cycloalkyl are preferably monocyclic C3-io-cycloalkyls such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, but include also polycyclic C3-io-cycloalkyls such as decalinyl, norbornyl and adamantyl.
Examples of Cs-io-cycloalkenyl are preferably monocyclic Cs-io-cycloalkenyls such as cyclopen- tenyl, cyclohexenyl, cyclohexadienyl and cycloheptatrienyl, but include also polycyclic
Cs-io-cycloalkenyls. Examples of monovalent 3 to 14 membered aliphatic heterocyclic residues are monocyclic monovalent 3 to 8 membered aliphatic cyclic residues and polycyclic, for example bicyclic monovalent 7 to 12 membered aliphatic heterocyclic residues.
Examples of monocyclic monovalent 3 to 8 membered aliphatic heterocyclic residues are mon- ocyclic monovalent 5 membered aliphatic heterocyclic residues containing one heteroatom such as pyrrolidinyl, 1 -pyrrolinyl, 2-pyrrolinyl, 3-pyrrolinyl, tetrahydrofuryl, 2,3-dihydrofuryl, tetrahy- drothiophenyl and 2,3-dihydrothiophenyl, monocyclic monovalent 5 membered aliphatic heterocyclic residues containing two heteroatoms such as imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, oxazolidinyl, oxazolinyl, isoxazolidinyl, isoxazolinyl, thiazolidinyl, thiazolinyl, isothia- zolidinyl and isothiazolinyl, monocyclic monovalent 5 membered aliphatic heterocyclic residues containing three heteroatoms such as 1 ,2,3-triazolyl, 1 ,2,4-triazolyl and 1 ,4,2-dithiazolyl, monocyclic monovalent 6 membered aliphatic heterocyclic residues containing one heteroatom such as piperidyl, piperidino, tetrahydropyranyl, pyranyl, thianyl and thiopyranyl, monocyclic monovalent 6 membered aliphatic heterocyclic residues containing two heteroatoms such as piperaz- inyl, morpholinyl and morpholino and thiazinyl, monocyclic monovalent 7 membered aliphatic heterocyclic residues containing one hereoatom such as azepanyl, azepinyl, oxepanyl, thi-
epanyl, thiapanyl, thiepinyl, and monocyclic monovalent 7 membered aliphatic heterocyclic residues containing two hereoatom such as 1 ,2-diazepinyl and 1 ,3-thiazepinyl.
An example of a bicyclic monovalent 7-12 membered aliphatic heterocyclic residue is decahy- dronaphthyl.
C6-i4-aryl can be monocyclic or polycyclic. Examples of C6-i4-aryl are monocyclic C6-aryl such as phenyl, bicyclic Cg-io-aryl such as 1 -naphthyl, 2-naphthyl, indenyl, indanyl and tetrahy- dronaphthyl, and tricyclic Ci2-i4-aryl such as anthryl, phenanthryl, fluorenyl and s-indacenyl.
The monovalent 5 to 14 membered aromatic heterocyclic residues can be monocyclic monovalent 5 to 8 membered aromatic heterocyclic residues, or polycyclic, for example bicyclic mono- valent 7 to 12 membered, tricyclic monovalent 9 to 14 membered aromatic heterocyclic residue, or tetracyclic monovalent 9 to 14 membered aromatic heterocyclic residues.
Examples of monocyclic monovalent 5 to 8 membered aromatic heterocyclic residues are mon- ocyclic monovalent 5 membered aromatic heterocyclic residues containing one heteroatom such as pyrrolyl, furyl and thiophenyl, monocyclic monovalent 5 membered aromatic heterocyclic residues containing two heteroatoms such as imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thia- zolyl, isothiazolyl, monocyclic monovalent 5 membered aromatic heterocyclic residues containing three heteroatoms such as 1 ,2,3-triazolyl, 1 ,2,4-triazolyl and oxadiazolyl, monocyclic mono- valent 5 membered aromatic heterocyclic residues containing four heteroatoms such as tetra- zolyl, monocyclic monovalent 6 membered aromatic heterocyclic residues containing one heteroatom such as pyridyl, monocyclic monovalent 6 membered aromatic heterocyclic residues containing two heteroatoms such as pyrazinyl, pyrimidinyl and pyridazinyl, monocyclic monovalent 6 membered aromatic heterocyclic residues containing three heteroatoms such as
1 ,2,3-triazinyl, 1 ,2,4-triazinyl and 1 ,3,5-triazinyl, monocyclic monovalent 7 membered aromatic heterocyclic residues containing one heteroatom such as azepinyl, and monocyclic monovalent 7 membered aromatic heterocyclic residues containing two heteroatoms such as 1 ,2-diazepinyl,
Examples of bicyclic monovalent 7 to 12 membered aromatic heterocyclic residues are bicyclic monovalent 8 membered aromatic heterocyclic residues containing two heteroatoms such as thieno[3,2-b]thiophenyl, bicyclic 9 membered aromatic heterocyclic residues containing one heteroatom such as indolyl, isoindolyl, indolizinyl, indolinyl, benzofuryl, isobenzofuryl, ben- zothiophenyl and isobenzothiophenyl, bicyclic monovalent 9 membered aromatic heterocyclic residues containing two heteroatoms such as indazolyl, benzimidazolyl, benzimidazolinyl, ben- zoxazolyl, benzisooxazolyl, benzthiazolyl, benzisothiazolyl, furopyridyl and thienopyridyl, bicyclic monovalent 9 membered aromatic heterocyclic residues containing three heteroatoms such as benzotriazolyl, benzoxadiazolyl, oxazolopyridyl, isooxazolopyridyl, thiazolopyridyl, isothia-
zolopyridyl and imidazopyridyl, bicyclic monovalent 9 membered aromatic heterocyclic residues containing four heteroatoms such as purinyl, bicyclic monovalent 10 membered aromatic heterocyclic residues containing one heteroatom such as quinolyl, isoquinolyl, chromenyl and chromanyl, bicyclic monovalent 10 membered aromatic heterocyclic residues containing two heteroatoms such as quinoxalinyl, quinazolinyl, cinnolinyl, phthalazinyl, 1 ,5-naphthyridinyl and 1 ,8-naphthyridinyl, bicyclic monovalent 10 membered aromatic heterocyclic residues containing three heteroatoms such as pyridopyrazinyl, pyridopyrimidinyl and pyridopyridazinyl, and bicyclic monovalent 10 membered aromatic heterocyclic residues containing four heteroatoms such as pteridinyl.
Examples of tricyclic monovalent 9 to 14 membered aromatic heterocyclic residues are dibenzo- furyl, acridinyl, phenoxazinyl, 7H-cyclopenta[1 ,2-b:3,4-b']dithiophenyl and 4H-cyclopenta- [2,1 -b:3,4-b']dithiophenyl. An example of a tricyclic monovalent 9 to 14 membered aromatic heterocyclic residue containing three heteroatoms is dithienothiophenyl of formula
An example of a tetracyclic monovalent 9 to 14 membered aromatic heterocyclic residue containing four heteroatoms is trithienothiophenyl of formula
Examples of halogen are -F, -CI, -Br and -I.
Examples of Ci-10-alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, fert-butoxy, n-pentoxy, neopentoxy, isopentoxy, hexoxy, n-heptoxy, n-octoxy, n-nonoxy and n-decoxy. Examples of Ci-30-alkoxy are Ci-10-alkoxy, and n-undecoxy,
n-dodecoxy, n-undecoxy, n-dodecoxy, n-tridecoxy, n-tetradecoxy, n-pentadecoxy, n-hexa- decoxy, n-heptadecoxy, n-octadecoxy, n-nonadecoxy and n-icosoxy (C20), n-docosoxy (C22), n-tetracosoxy (C24), n-hexacosoxy (C26), n-octacosoxy (C28) and n-triacontoxy (C30).
Examples of C2-6-alkylene are ethylene, butylene, pentylene, hexylene and 2-methylpentylene.
Examples of C6-i4-arylene are monocyclic C6-arylene such as phenylene, bicyclic Cg-io-arylene such as naphthylene, for example
indenylene, for example
*
indanylene, for example
*
and tetrahydronaphthylene, for example
*
and tricyclic Ci2-i4-arylene such as anthrylene, for example
phenanthrylene, for example
fluorenylene, for example
and
s-indacenylene, for example
Examples of C6-24-arylene are C6-i4-arylene and
pyrenylene, for example
* tetracenylene, for example
pentacenylene, for example
*
coronenylene, for example
*
and tetraphenylenylene, for example
The bivalent 5 to 14 membered aromatic heterocyclic residues can be monocyclic bivalent 5 to 8 membered aromatic heterocyclic residues, or polycyclic, for example bicyclic bivalent 7 to 14 membered, tricyclic bivalent 9 to 14 membered aromatic heterocyclic residues, or tetracyclic bivalent 9 to 14 membered aromatic heterocyclic residues.
Examples of monocyclic bivalent 5 to 8 membered aromatic heterocyclic residues are monocyclic bivalent 5 membered aromatic heterocyclic residues containing one heteroatom such as pyr- rolylene, furylene and thiophenylene, monocyclic bivalent 5 membered aromatic heterocyclic residues containing two heteroatoms such as imidazolylene, pyrazolylene, oxazolylene, isoxa- zolylene, thiazolylene, isothiazolylene, monocyclic bivalent 5 membered aromatic heterocyclic residues containing three heteroatoms such as 1 ,2,3-triazolylene, 1 ,2,4-triazolylene and oxadia- zolylene, monocyclic bivalent 5 membered aromatic heterocyclic residues containing four heteroatoms such as tetrazolylene, monocyclic bivalent 6 membered aromatic heterocyclic residues containing one heteroatom such as pyridylene, monocyclic bivalent 6 membered aromatic heterocyclic residues containing two heteroatoms such as pyrazinylene, pyrimidinylene and pyridazinylene, monocyclic bivalent 6 membered aromatic heterocyclic residues containing three heteroatoms such as 1 ,2,3-triazinylene, 1 ,2,4-triazinylene and 1 ,3,5-triazinylene, monocyclic bivalent 7 membered aromatic heterocyclic residues containing one heteroatom such as azepinylene, and monocyclic bivalent 7 membered aromatic heterocyclic residues containing two heteroatoms such as 1 ,2-diazepinylene.
Examples of bicyclic bivalent 7 to 14 membered aromatic heterocyclic residues are
bicyclic bivalent 8 membered aromatic heterocyclic residues containing two heteroatoms such as thienothiophenylene, for example
bicyclic bivalent 8 membered aromatic heterocyclic residues containing three heteroatoms such as as thienothiazolylene, for example
bicyclic bivalent 8 membered aromatic heterocyclic residues containing four heteroatoms such as thiazothiazolylene, for example
bicyclic bivalent 9 membered aromatic heterocyclic residues containing one heteroatom such as indolylene, isoindolylene, indolizinylene, indolinylene, isoindolinylene, for example
1 ,8-naphthyridinylene, bicyclic bivalent 10 membered aromatic heterocyclic residues containing three heteroatoms such as pyridopyrazinylene, pyridopyrimidinylene and pyridopyridazinylene, and bicyclic bivalent 10 membered aromatic heterocyclic residues containing four heteroatoms such as pterid- inylene. Examples of tricyclic bivalent 9 to 14 membered aromatic heterocyclic residues containing one heteroatom are dibenzofurylene, acridinylene, dibenzosilacyclopentadienylene, for example
Examples of a tricyclic bivalent 9 to 14 membered aromatic heterocyclic residues containing two heteroatoms are phenoxazinylene, and the following compounds
Examples of tricyclic bivalent 9 to 14 membered aromatic heterocyclic residue containing three heteroatoms are the following compounds
Examples of tricyclic bivalent 9 to 14 membered aromatic heterocyclic residue containing four- heteroatoms are the following compounds
An example of a tricyclic bivalent 9 to 14 membered aromatic heterocyclic residue containing heteroatoms is the following compound
Examples of bivalent 5 to 24 membered aromatic heterocyclic residues are bivalent 5 to 14 membered aromatic heterocyclic residues, and the following compounds
Examples of L are:
In preferred units of formula (1 )
R1 and R2 are independently from each other H, Ci-30-alkyl optionally substituted with 1 to 6 substituents Rc, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rc, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rc, -io-cycloalkyl optionally substituted with 1 to 6 substituents Rd, Cs-io-cycloalkenyl or -i4-aryl optionally substituted with 1 to 6 substituents Re, wherein Rc at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -O-COR3, -S-Ci-10-alkyl, -NH2, -NHR3, -NR3R4, -NH-COR3, -COOH, -COOR3, -CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
Rd at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -O-COR3, -S-Ci-10-alkyl, -NH2, -NHR3, -NR3R4, -NH-COR3, -COOH, -COOR3, -CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, Ci-10-alkyl, C2-io-alkenyl,
C2-io-alkynyl, -i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
Re at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -O-COR3, -S-Ci-10-alkyl, -NH2, -NHR3, -NR3R4, -NH-COR3, -COOH, -COOR3, -CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, Ci-10-alkyl, C2-io-alkenyl,
C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl and monovalent 3 to 14 membered aliphatic heterocyclic residue, wherein R3 and R4 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl,
Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue,
G1 and G2 are independently from each other -i4-arylene optionally substituted with 1 to 6 substituents Ra or bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Ra, wherein
Ra at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-30-alkoxy,
-0-CH2CH20-Ci-3o-alkyl, -O-COR8, -S-Ci-3o-alkyl, -NH2, -NHR8, -NR8R9, -NH-COR8, -COOH, -COOR8, -CONH2, -CONHR8, -CONR8R9, -CO-H, -COR8, Ci-so-alkyl optionally substituted with 1 to 6 substituents Rf, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rf, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rf, C3-io-cycloalkyl optionally substituted with 1 to 6 substituents Rs, Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents Rs and monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents Rs, wherein
R8 and R9 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
Rf at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR 0R11, -NH-COR10, -COOH, -COOR10, -CONH2, -CONHR10, -CONR 0R11, -CO-H, -COR10, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
Ra at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-e-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR 0R11, -NH-COR10,
-COOH, -COOR10, -CONH2, -CONHR10, -CONR 0R11, -CO-H, -COR10, Ci-10-alkyl,
C2-io-alkenyl, C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R10 and R1 1 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
G1 and G2 are independently from each other
R5 and R6 are independently from each other H or Ci
L is C6-24-arylene optionally substituted with 1 to 6 substituents Rb or bivalent 5 to 24 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Rb, wherein
Rb at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN , -N02, -OH , Ci-30-alkoxy,
-0-CH2CH20-Ci-3o-alkyl, -O-COR12, -S-Ci-3o-alkyl, -N H2, -N H R12, -N R12R13, -N H-COR12, -COOH , -COOR12, -CON H2, -CON H R 2, -CON R 2R13, -CO-H , -COR12, Ci-30-alkyl optionally substituted with 1 to 6 substituents Rh, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rh, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rh, C3-io-cyclo- alkyl optionally substituted with 1 to 6 substituents R', Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents R' and monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents R', wherein
R12 and R13 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
Rh at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -NO2, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR14, -S-Ci-io-alkyl, -NH2, -NHR14, -NR14R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR 4, -CONR R15, -CO-H, -COR14, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
R' at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR14, -CONR R15, -CO-H, -COR14, Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R14 and R15 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
R16 and R17 are independently from each other H, Ci-30-alkyl, -CN or halogen,
q and s are independently from each other 0, 1 , 2, 3, 4 or 5, r is 0, 1 or 2, and n is an integer from 2 to 10Ό00.
In more preferred units of formula (1 )
R1 and R2 are independently from each other Ci-30-alkyl optionally substituted with 1 to 6 substituents Rc, preferably Ci -alkyl optionally substituted with 1 to 6 substituents Rc, more preferably Ci-12-alkyl optionally substituted with 1 to 6 substituents Rc, wherein
Rc at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -0-COR3, -S-Ci-10-alkyl, -NH2, -NHR3, -NR3R4, -NH-COR3, -COOH, -COOR3, -CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R3 and R4 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, -io-cycloalkyl, -io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue,
-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue,
G1 and G2 are independently from each other -i4-arylene optionally substituted with 1 to 6 substituents Ra or bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Ra, wherein
Ra at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C -alkylene-0-, halogen, -CN, -N02, -OH, Ci-30-alkoxy,
-0-CH2CH20-Ci-3o-alkyl, -O-COR8, -S-Ci-3o-alkyl, -NH2, -NHR8, -NR8R9, -NH-COR8, -COOH, -COOR8, -CONH2, -CONHR8, -CONR8R9, -CO-H, -COR8, Ci-so-alkyl optionally substituted with 1 to 6 substituents Rf, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rf, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rf, -io-cycloalkyl optionally substituted with 1 to 6 substituents Rs, Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents Rs and monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents Rs, wherein
R8 and R9 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, -io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
Rf at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR10R11, -NH-COR10 -COOH, -COOR10, -CONH2, -CONHR10, -CONR 0R11, -CO-H, -COR10, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
R9 at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR 0R11, -NH-COR10 -COOH, -COOR10, -CONH2, -CONHR10, -CONR 0R11, -CO-H, -COR10, Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R10 and R11 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-10- cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
G1 and G2 are independently from each other
R5 and R6 are independently from each other H or Ci-30-alkyl,
L is C6-24-arylene optionally substituted with 1 to 6 substituents Rb or bivalent 5 to 24 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Rb, wherein
Rb at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-30-alkoxy,
-0-CH2CH20-Ci-3o-alkyl, -O-COR12, -S-Ci-30-alkyl, -NH2, -NHR12, -NR 2R13, -NH-COR12, -COOH, -COOR12, -CONH2, -CONHR12, -CONR 2R13, -CO-H, -COR12, Ci-30-alkyl optionally substituted with 1 to 6 substituents Rh, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rh, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rh, C3-io-cyclo-
alkyl optionally substituted with 1 to 6 substituents R', Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents R' and monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents R', wherein
R12 and R13 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
Rh at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-e-alkylene-0-, halogen, -CN, -NO2, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -0-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR14R15, -NH-COR14 -COOH, -COOR14, -CONH2, -CONHR 4, -CONR R15, -CO-H, -COR14, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
R' at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -0-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR 4R15, -NH-COR14 -COOH, -COOR14, -CONH2, -CONHR14, -CONR R15, -CO-H, -COR14, Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, -i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R14 and R15 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl,
C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
R16 and R17 are independently from each other H, Ci-30-alkyl, -CN or halogen,
q and s are independently from each other 0, 1 , 2, 3, 4 or 5, r is 0, 1 or 2, and n is an integer from 2 to 10Ό00.
In even more preferred units of formula (1 )
R1 and R2 are independently from each other Ci-30-alkyl optionally substituted with 1 to 6 sub- stituents Rc, preferably Ci-16-alkyl optionally substituted with 1 to 6 substituents Rc, more preferably Ci-12-alkyl optionally substituted with 1 to 6 substituents Rc, wherein
Rc at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -O-COR3, -S-Ci-10-alkyl, -NH2, -NHR3, -NR3R4, -NH-COR3, -COOH, -COOR3, -CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R3 and R4 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, C5-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue,
G1 and G2 are independently from each other bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Ra, wherein
Ra at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-30-alkoxy,
-0-CH2CH20-Ci-3o-alkyl, -O-COR8, -S-Ci-3o-alkyl, -NH2, -NHR8, -NR8R9, -NH-COR8, -COOH, -COOR8, -CONH2, -CONHR8, -CONR8R9, -CO-H, -COR8, Ci-so-alkyl optionally substituted with 1 to 6 substituents Rf, C2-3o-alkenyl optionally substituted with 1 to 6 sub- stituents Rf, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rf, C3-io-cycloalkyl optionally substituted with 1 to 6 substituents Rs, Cs-io-cycloalkenyl optionally substituted
with 1 to 6 substituents Rs and monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents Rs, wherein
R8 and R9 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cyclo- alkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue, Rf at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR10R11, -NH-COR10, -COOH, -COOR10, -CONH2, -CONHR10, -CONR 0R11, -CO-H, -COR10, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monova- lent 5 to 14 membered aromatic heterocyclic residue; at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR 0R11, -NH-COR10, -COOH, -COOR10, -CONH2, -CONHR10, -CONR 0R11, -CO-H, -COR10, Ci-10-alkyl,
C2-io-alkenyl, C2-io-alkynyl, -i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R10 and R11 at each occurrence are independently from each other se- lected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl,
-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue, or
G1 and G2 are independently from each other
R5 and R6 are independently from each other H or Ci-30-alkyl,
L is bivalent 5 to 24 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Rb, wherein
Rb at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-30-alkoxy,
-0-CH2CH20-Ci-3o-alkyl, -O-COR12, -S-Ci-3o-alkyl, -NH2, -NHR12, -NR12R13, -NH-COR12, -COOH, -COOR12, -CONH2, -CONHR 2, -CONR 2R13, -CO-H, -COR12, Ci-so-alkyl optionally substituted with 1 to 6 substituents Rh, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rh, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rh, C3-io-cyclo- alkyl optionally substituted with 1 to 6 substituents R', Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents R' and monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents R', wherein
R12 and R13 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
Rh at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR14, -CONR R15, -CO-H, -COR14, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
R' at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR R15, -NH-COR14,
-COOH, -COOR14, -CONH2, -CONHR14, -CONR R15, -CO-H, -COR14, Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, -i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R14 and R15 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
or
R16 and R17 are independently from each other H, Ci-30-alkyl, -CN or halogen,
q and s are independently from each other 0, 1 , 2, 3, 4 or 5, r is 0, 1 or 2, and n is an integer from 2 to 10Ό00.
In most preferred units of formula (1 )
R1 and R2 are independently from each other Ci-16-alkyl, more preferably Ci-12-alkyl,
G1 and G2 are independently from each other monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue optionally substituted with 1 to 4 substituents Ra, wherein
Ra at each occurrence are independently from each other Ci-30-alkyl optionally substituted with 1 to 4 substituents Rf, wherein
Rf at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR10R11, -NH-COR10, -COOH, -COOR10, -CONH2, -CONHR10, -CONR 0R11, -CO-H, -COR10, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent
5 to 14 membered aromatic heterocyclic residue;
L is bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 4 substituents Rb, wherein
Rb at each occurrence are independently from each other Ci-30-alkyl optionally substituted with 1 to 4 substituents Rh, wherein
Rh at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR14R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR 4, -CONR R15, -CO-H, -COR14, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
q and s are independently from each other 1 , 2 or 3, r is 1 or 2, and n is an integer from 5 to 10Ό00.
In even most preferred units of formula (1 )
R1 and R2 are independently from each other Ci-16-alkyl, more preferably Ci-i2-alkyl, G1 and G2 are independently from each other monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue, wherein G1 and G2 are substituted with 1 to 2 substituents Ra, wherein
Ra at each occurrence are independently from each other C6-2o-alkyl,
L is bivalent 5 to 14 membered aromatic heterocyclic residue, wherein L is substituted with 1 to 2 substituents Rb, wherein
Rb at each occurrence are independently from each other C6-2o-alkyl, q and s are both 1 ,
r is 1 , and n is an integer from 5 to 10Ό00.
Particular preferred units of formula (1 ) are units of formula
wherein R1, R2, Ra, L and n are as defined above.
In particular preferred units of formula (1a)
L is
Preferably, n is an integer from 5 to 5Ό00, more preferably from 5 to 1 Ό00, even more preferably from 5 to 100, and most preferably from 10 to 100.
A particular preferred example of the units of formulae (1 ) and (1a) is the unit of formula
Most preferably, the semiconducting material of the present invention is a polymer consisting essentially of a unit of formula (1 ), respectively, (1a).
The polymer comprising a unit of formula (1 ) can be prepared by treating a compound of formula
wherein R1, R2, G1, G2, q and s are as defined above, and Hal1 is halogen, preferably -Br, with a compound of formula
(3)
Transition metal catalyst 1 is preferably a palladium catalyst such tris(dibenzylideneacetone)- dipalladium(O), preferably in combination with a phosphine such as tri-otolylphosphine. The reaction is preferably performed at elevated temperatures such 80 to 200 °C, preferably 90 to 150 °C. The reaction can be performed in an inert organic solvent such as chlorobenzene. The reaction can be stopped by the addition of end cappers such as 2-bromothiophene and 2-thiophene boronic acid. The crude product may be worked up by conventional methods, for example by extracting the crude product with an appropriate solvent, for example with acetone.
The compound of formula (2) can be prepared by treating a compound of formula
The halogenating agent is preferably /V-bromosuccinimide. The reaction is preferably performed at ambient temperatures such -5 to 50 °C, preferably 0 to 30 °C. The reaction can be performed in an organic solvent such chloroform. The crude product may be worked up by conventional methods, for example by column chromatography.
The compound of formula (4) can be prepared by reacting a compound of formula
(6) wherein G1, G2, q and s are as defined above, and R200, R201 and R202 are independently from each other Ci-10-alkyl, preferably methyl in the presence of a transition metal catalyst 2.
Transition metal catalyst 2 is preferably a palladium catalyst such tetrakis(triphenylphosphine) palladium(O). The reaction is preferably performed at elevated temperatures such 80 to 200 °C, preferably 90 to 150 °C. The reaction can be performed in an inert organic solvent such as di- methylformamide. The crude product may be worked up by conventional methods, for example by column chromatography. The compound of formula (5) can be prepared by treating a compound of formula
The halogenating agent is preferably Br2. The reaction is preferably performed at ambient temperatures such -5 to 30 °C, preferably 0 to 30 °C. The reaction can be performed in an organic solvent such dichloromethane. The crude product may be worked up by conventional methods.
The compound of formula (8) can be prepared according to following reaction scheme:
(12) (11)
The compounds of formulae (2), (4) and (5) are also part of the invention.
Also part of the present invention is an electronic device comprising the polymer comprising a unit of formula (1 ) as semiconducting material. Preferably, the electronic device is an organic field effect transistor (OFET), and in particular a thin film transistor (TFT). Preferably, the elec- tronic device is an organic photovoltaic device (OPV).
Usually, an organic field effect transistor comprises a dielectric layer, a semiconducting layer and a substrate. In addition, on organic field effect transistor usually comprises a gate electrode and source/drain electrodes.
An organic field effect transistor can have various designs.
The most common design of a field-effect transistor is the Bottom-Gate Top-Contact (BGTC) design. Here, the gate is on top of the substrate and at the bottom of the dielectric layer, the semiconducting layer is at the top of the dielectric layer and the source/drain electrodes are on top of the semiconducting layer.
Another design of a field-effect transistor is the Top-Gate Bottom-Contact (TGBC) design. Here, the source/drain electrodes are on top of the substrate and at the bottom of the semiconducting layer, the dielectric layer is on top of the semiconducting layer and the gate electrode is on top of the dielectric layer.
The semiconducting layer comprises the semiconducting material of the present invention. The semiconducting layer can have a thickness of 5 to 500 nm, preferably of 10 to 100 nm, more preferably of 20 to 50 nm. The dielectric layer comprises a dielectric material. The dielectric material can be silici- um/silicium dioxide, or, preferably, an organic polymer such as polystyrene (PS), polymethylmethacrylate) (PMMA), poly(4-vinylphenol) (PVP), polyvinyl alcohol) (PVA), anzocyclobutene (BCB), or polyimide (PI). The dielectric layer can have a thickness of 10 to 2000 nm, preferably of 50 to 1000 nm, more preferably of 100 to 800 nm.
The source/drain contacts and the gate contact can be made from any suitable material, for example Au.
The substrate can be any suitable substrate such as glass, or a plastic substrate. Preferably the substrate is a plastic substrate such as polyethersulfone, polycarbonate, polysulfone, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). More preferably, the plastic substrate is a plastic foil.
The organic field effect transistor can be prepared by methods known in the art.
For example, a top-gate bottom-contact (TGBC) thin film transistors (TFTs) can be prepared as follows: first: the source/drain contacts are placed on the substrate, for example by thermal evaporation of the source/drain material; second: the substrate is coated with the semiconduct- ing layer, for example by spin-coating a solution of the semiconducting material in a suitable solvent and drying the semiconducting layer at elevated temperatures, for example at 80 to 100 °C; third: the semiconducting layer is coated with a solution of the dielectric material in a suitable solvent, for example by spin-coating a solution of the dielectric material and drying the dielectric layer at elevated temperatures, for example at 80 to 100 °C; fourth: the gate contact is placed on top of the dielectric layer, for example by thermal evaporation of the gate material.
Also part of the present invention is the use of the polymer comprising the unit of formula (1 ) as semiconducting material.
Electronic devices comprising the semiconducting materials of the present invention show high charge carrier mobility as well as high stability, in particular towards oxidation by air, under ambient environmental conditions.
In addition, the semiconducting materials of the present invention are compatible with liquid processing techniques such as spin coating and thus allow the production of low cost, light weight and flexible electronic devices.
Examples
Example 1
Preparation of polymer P1 essentially consisting of units of formula (1 b) The polymer P1 essentially consisting of units of formula (1 b) is prepared according to the following reaction scheme:
(2a) (1b)
Preparation of the compound of formula (1 1a)
Methyl iodide (10.9 g, 76.8 mmol) is added to a solution of 1 ,5-naphthyridine (12) (5 g, 38.4 mmol) in MeOH (30 mL) and the reaction mixture is heated at 40 °C over 3 days under N2. The precipitate is filtered and dried under high vacuum to afford compound 1 1a as yellowish green solid (8.51 g, 81 .1 %). 1H NMR (400 MHz, CDCI3, r.t) δ 9.49 (d, 1 H), 9.38 (dd, 1 H), 9.26 (d, 1 H), 8.98 (dd, 1 H), 4.75 (s, 3H).
Preparation of the compound of formula (10a)
NaOH solution (5.6 g, 140.2 mmol, in 30 mL H20) and K3Fe(CN)6 solution (21 .6 g, 65.5 mmol, in 30 mL H2O) are added concurrently over 30 min to a solution of napthyridine methiodide (1 1a) (8.5 g, 31 .2 mmol) in H2O (80 mL) at -10 °C. The reaction mixture is allowed to warm to RT overnight. Excess NaCI is added and the reaction mixture is then extracted with CHC (150 mL x 3). The combined organic phases are dried over Na2S04, filtered and concentrated in vacuo. The crude product is purified by flash column using MeOH+1 % TEA on silica gel to afford compound 10a as violet solid (3.07 g, 61.4 %). 1H NMR (400 MHz, CD3OD, r.t) δ 12.49 (d, 1 H), 12.00 (d, 1 H), 1 1.91 (d, 1 H), 1 1.59 (dd, 1 H), 10.88 (d, 1 H), 8.79 (s, 3H).
Preparation of the compound of formula (9a)
Mel (3.58 mL, 57.5 mmol) is added to a solution of compound 10a (3.07 g, 19.2 mmol) in toluene (50 mL) and the reaction mixture is allowed to stir at 1 15°C for 2 days. The reaction mixture is filtered and dried in vacuo to afford compound 9a as green solid (4.75 g, 81 .8 %). 1H NMR (400 MHz, CD3OD, r.t) δ 8.95 (d, 1 H), 8.79 (d, 1 H), 8.50 (dd, 1 H), 8.19 (dd, 1 H), 7.34 (d, 1 H), 4.63 (s, 3H), 3.87 (s, 3H).
Preparation of the compound of formula (8a)
NaOH solution (4.39 g, 109.7 mmol, in 15 mL H20) and K3Fe(CN)6 solution (15.51 g,
47.1 mmol, in 50 mL of water ) are added concurrently over 30 min to a solution of methyl- napthyridine methiodide 9a (4.75 g, 15.7 mmol) in H2O (25 mL) at 0 °C. The reaction mixture is allowed to stir at 0 °C for 30 min and is then allowed to warm to RT overnight. Excess NaCI is added followed by extraction with CHCb (100 mL x 3). The combined organic phases are dried over Na2S04 and concentrated in vacuo. Recrystallization in MeOH/Acetone mixture afforded compound 8a as orange brown crystals (1 .52 g, 51 .1 %). 1H NMR (400 MHz, CD3OD, r.t) δ 8.04 (d, 2H), 6.92 (d, 2H), 4.87 (s, 3 H), 3.80 (s, 3H).
Preparation of the compound of formula (5a)
1 ,5-dimethylnapthyridine-dione 8a (1 .35 g, 7.08 mmol), NaHCOs (2.38 g, 28.3 mmol) and bromine (2.83 g, 17.1 mmol) are dissolved in dichloromethane/H20 mixture (1 :1 , 200 mL) at 0 °C and allowed to warm to RT overnight. The reaction mixture is filtered and washed with MeOH. Saturated sodium thiosulfate (aq) is added to the filtrate and the aqueous phase is extracted with dichloromethane (200 mL x 3). The combined organic phases are dried over Na2S04 and concentrated in vacuo. The combined solids are dispersed in methanol, subjected to 3 cycles of
sonication, followed by centrifugation and decantation to yield yellow compound 5a (2.18 g, 88.5 %). H NMR (400 MHz, DMSO, r.t) δ 8.36 (s, 2H), 3.72 (s, 6H).
Preparation of the compound of formula (4a)
Pd(PPh3)4 (0.1 1 g, 0.10 mmol) is added to a solution of compound 5a (0.68 g, 1.97 mmol) and compounds 6a (2.45 g, 5.90 mmol) in degassed dimethylformamide (23 ml_). The reaction mixture is heated to 130 °C and stirred overnight. The reaction mixture is allowed to cool to RT, washed with H2O (25 ml_), extracted with CH2CI2 (25 ml. x 3), dried over Na2S04 and concentrated. The residue is purified by flash column (0→ 100% ethyl acetate/hexane) to afford com- pound 4a as red solid (0.42 g, 31 %). 1H NMR (400 MHz, CDCI3, r.t) δ 7.71 (s, 2H), 7.42 (d, 2H), 7.04 (d, 2H), 3.82 (s, 6H), 2.73 (t, 4H), 1 .67 - 1 .48 (m, 35H), 0.87 - 0.85 (m, 1 1 H).
Preparation of the compound of formula (2a)
/V-bromosuccinimide (0.17 g, 0.97 mmol) is added to a solution of compound 4a (0.32 g, 0.46 mmol) in CHCI3 (32 ml.) at 0 °C. The temperature of the reaction mixture is allowed to slowly rise to RT and the reaction mixture is stirred overnight. The reaction mixture is quenched with H2O (50 ml_), extracted with CHCI3 (50 ml. x 3), washed with brine, dried over Na?S04 and concentrated. Crude compound 2a is purified by flash column (0→ 50% ethyl acetate/hexane) to afford compound 2a as red solid (0.46 g, 88%). 1H NMR (400 MHz, CDCI3, r.t) δ 7.68 (s, 2H), 6.98 (s, 2H), 3.80 (s, 6H), 2.69 (t, 4H), 1 .68 - 1 .56 (m, 35H), 0.88 - 0.84 (m, 1 1 H).
Preparation of polymer P1 essentially consisting of units of formula (1 b)
Compound 2a (100 mg, 0.12 mmol), compound 3a (1 12 mg, 0.12 mmol), Pd2dba3 (5.4 mg, 0.006 mmol) and P(o-tolyl)3 (3.6 mg, 0.01 mmol) are added to a Schlenk tube and degassed 3 times with nitrogen. Chlorobenzene (3 ml.) is then added and the reaction mixture is heated under N2 at 130 °C. After 2 days, 1 drop of 2-bromothiophene is added and the reaction mixture is allowed to stir for 1 h. 1 drop of 2-(tributylstannyl)thiophene is added and the reaction mixture is allowed to stir at 130 °C overnight. The reaction mixture is poured slowly into 500 ml. of MeOH. The mixture is stirred for 2 h. The precipitate obtained is filtered and subjected to Sox- hlet extraction with acetone overnight. The filtrate is dried under vacuo, dissolved in minimum amount of hot chlorobenzene and precipitated again by pouring it into beaker with methanol. The mixture is stirred for 1 h, filtered and the filtrate is dried under vacuum overnight to afforded polymer P1 as red solid (36 mg, 23 %). 1H NMR (400 MHz, DCE, r.t) δ 7.72 (brs, 2 H), 7.22 - 7.12 (m, 4H), 3.83 (brs, 6 H), 2.80 (brs, 4H), 1.79 - 0.85 (m, 1 12H). Mn: 1 .24 x 104, PDI: 2.53.
Example 2
Preparation of top-gate bottom-contact transistors (TGBC) containing the polymer P1 , essentially consisting of the units of formula 1 b, as semiconducting material A top-gate bottom-contact (TGBC) thin film transistor (TFT) is fabricated on glass (PGO glass used as received). Au source-drain contacts (30 nm-thick) are thermally-evaporated. The substrate is then coated with the semiconductor layer (thickness: 40 to 50 nm) by spin-coating (1000 rpm) a solution of polymer P1 (prepared as described in example 1 ) in dichloromethane (concentration ~ 10 mg/mL), and drying the film at 90 °C for 30 seconds. A 4 weight% polysty- rene solution in isopropyl acetate is spin-coated (3600 rpm) and the dielectric film formed is dried at 90 °C for 30 seconds to yield a dielectric layer (thickness: 500 to 600 nm). The device structure is completed by vapor deposition of patterned Au gate contacts (-30 nm thick) through a shadow mask. Channel lengths and widths are 50 μηη and 0.5 mm, respectively, to afford W/L = 10.
The top-gate, bottom-contact (TGBC) thin film transistors of example 2 show the following mobility: 4 x 10-3 cm2V-1s-1.
Claims
1 . A polymer comprising a unit of formula
R1 and R2 are independently from each other H , Ci-30-alkyl optionally substituted with 1 to 6 substituents Rc, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rc, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rc, C3-io-cycloalkyl optionally substituted with 1 to 6 substituents Rd, Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents Rd, monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents Rd, C6-i4-aryl optionally substituted with 1 to 6 substituents Re or monovalent 5 to14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Re, wherein Rc at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN , -N02, -OH , Ci-10-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -O-COR3, -S-Ci-10-alkyl, -N H2, -N H R3, -N R3R4, -N H-COR3, -COOH , -COOR3, -CON H2, -CON H R3, -CON R3R4, -CO-H , -COR3, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
Rd at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN , -NO2, -OH , Ci-10-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -O-COR3, -S-Ci-10-alkyl, -N H2, -N H R3, -N R3R4, -N H-COR3, -COOH , -COOR3, -CON H2, -CON H R3, -CON R3R4, -CO-H , -COR3, Ci-10-alkyl, C2-io-alkenyl,
C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
Re at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN , -NO2, -OH , Ci-10-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -O-COR3, -S-Ci-10-alkyl, -N H2, -N H R3, -N R3R4, -N H-COR3, -COOH , -COOR3, -CON H2, -CON H R3, -CON R3R4, -CO-H , -COR3, Ci-10-alkyl, C2-io-alkenyl,
C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl and monovalent 3 to 14 membered aliphatic heterocyclic residue, wherein R3 and R4 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cyclo- alkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue,
G1 and G2 are independently from each other -i4-arylene optionally substituted with 1 to 6 substituents Ra or bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Ra, wherein
Ra at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-30-alkoxy,
-0-CH2CH20-Ci-3o-alkyl, -O-COR8, -S-Ci-3o-alkyl, -NH2, -NHR8, -NR8R9, -NH-COR8, -COOH, -COOR8, -CONH2, -CONHR8, -CONR8R9, -CO-H, -COR8, Ci-so-alkyl optionally substituted with 1 to 6 substituents Rf, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rf, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rf, C3-io-cycloalkyl optionally substituted with 1 to 6 substituents Rs, Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents Rs and monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents Rs, wherein
R8 and R9 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
Rf at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR 0R11, -NH-COR10, -COOH, -COOR10, -CONH2, -CONHR10, -CONR 0R11, -CO-H, -COR10, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
Ra at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR 0R11, -NH-COR10, -COOH, -COOR10, -CONH2, -CONHR10, -CONR 0R11, -CO-H, -COR10, Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, -i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R10 and R11 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue, or
G1 and G2 are independently from each other
R5 and R6 are independently from each other H or Ci
is C6-24-arylene optionally substituted with 1 to 6 substituents Rb or bivalent 5 to 24 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Rb, wherein
Rb at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-30-alkoxy,
-0-CH2CH20-Ci-3o-alkyl, -O-COR12, -S-Ci-3o-alkyl, -NH2, -NHR12, -NR12R13, -NH-COR12, -COOH, -COOR12, -CONH2, -CONHR 2, -CONR 2R13, -CO-H, -COR12, Ci-so-alkyl optionally substituted with 1 to 6 substituents Rh, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rh, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rh, C3-io-cyclo- alkyl optionally substituted with 1 to 6 substituents R', Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents R' and monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents R', wherein
R12 and R13 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
Rh at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-e-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR14, -CONR R15, -CO-H, -COR14, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, -i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
R' at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR14R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR 4, -CONR R15, -CO-H, -COR14, Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, -i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R14 and R15 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue, or
L is
R16 and R17 are independently from each other H, Ci-30-alkyl, -CN or halogen, q and s are independently from each other 0, 1 , 2, 3, 4 or 5, r is 0, 1 or 2, and n is an integer from 2 to 10Ό00.
2. The polymer of claim 1 , wherein
R1 and R2 are independently from each other H, Ci-30-alkyl optionally substituted with 1 to 6 substituents Rc, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rc, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rc, C3-io-cycloalkyl optionally substituted with 1 to 6 substituents Rd, Cs-io-cycloalkenyl or C6-i4-aryl optionally substituted with 1 to 6 sub- stituents Re, wherein
Rc at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -0-COR3, -S-Ci-10-alkyl, -NH2, -NHR3, -NR3R4, -NH-COR3, -COOH, -COOR3, -CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
Rd at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -O-COR3, -S-Ci-10-alkyl, -NH2, -NHR3, -NR3R4, -NH-COR3, -COOH, -COOR3, -CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, Ci-10-alkyl, C2-io-alkenyl,
C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
Re at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -0-COR3, -S-Ci-10-alkyl, -NH2, -NHR3, -NR3R4, -NH-COR3, -COOH, -COOR3, -CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, Ci-10-alkyl, C2-io-alkenyl,
C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl and monovalent 3 to 14 membered aliphatic heterocyclic residue, wherein R3 and R4 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue.
3. The polymer of claim 1 , wherein
R1 and R2 are independently from each other Ci-30-alkyl optionally substituted with 1 to 6 substituents Rc, wherein
Rc at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -0-COR3, -S-Ci-10-alkyl, -NH2, -NHR3, -NR3R4, -NH-COR3, -COOH, -COOR3, -CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R3 and R4 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, C5-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue.
4. The polymer of claim 1 , wherein
R1 and R2 are independently from each other Ci-16-alkyl, more preferably Ci-12-alkyl.
5. The polymer of any of claims 1 to 4, wherein
G1 and G2 are independently from each other bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Ra, wherein
Ra at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-30-alkoxy,
-0-CH2CH20-Ci-3o-alkyl, -O-COR8, -S-Ci-3o-alkyl, -NH2, -NHR8, -NR8R9, -NH-COR8, -COOH, -COOR8, -CONH2, -CONHR8, -CONR8R9, -CO-H, -COR8, Ci-so-alkyl optionally substituted with 1 to 6 substituents Rf, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rf, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rf, C3-io-cycloalkyl optionally substituted with 1 to 6 substituents Rs, Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents Rs and monovalent 3 to 14 membered aliphatic heterocyclic resi- due optionally substituted with 1 to 6 substituents Rs, wherein
R8 and R9 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cyclo- alkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
Rf at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR 0R11, -NH-COR10,
-COOH, -COOR10, -CONH2, -CONHR10, -CONR 0R11, -CO-H, -COR10, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue;
Ra at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR 0R11, -NH-COR10, -COOH , -COOR10, -CON H2, -CON H R10, -CON R 0R1 1 , -CO-H , -COR10, Ci-io-alkyl, C2-io-alkenyl, C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R10 and R1 1 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
G1 and G2 are independently from each other
R5 and R6 are independently from each other H or Ci-30-alkyl.
6. The polymer of any of claims 1 to 4, wherein
G1 and G2 are independently from each other monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue optionally substituted with 1 to 4 substituents Ra, wherein
Ra at each occurrence are independently from each other Ci-30-alkyl optionally substituted with 1 to 4 substituents Rf, wherein
Rf at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN , -NO2, -OH , Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR10, -S-Ci-10-alkyl, -N H2, -N H R10, -N R10R1 1 , -N H-COR10, -COOH , -COOR10, -CON H2, -CON H R10, -CON R 0R1 1 , -CO-H , -COR10, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue.
7. The polymer of any of claims 1 to 4, wherein
G1 and G2 are independently from each other monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue, wherein G1 and G2 are substituted with 1 to 2 substituents Ra, wherein
Ra at each occurrence are independently from each other C6-2o-alkyl.
8. The polymer of any of claims 1 to 7, wherein
L is bivalent 5 to 24 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Rb, wherein
Rb at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-30-alkoxy,
-0-CH2CH20-Ci-3o-alkyl, -O-COR12, -S-Ci-3o-alkyl, -NH2, -NHR 2, -NR12R13, -NH-COR12, -COOH, -COOR12, -CONH2, -CONHR 2, -CONR 2R13, -CO-H, -COR12, Ci-so-alkyl optionally substituted with 1 to 6 substituents Rh, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rh, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rh, C3-io-cyclo- alkyl optionally substituted with 1 to 6 substituents R', Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents R' and monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents R', wherein
R12 and R13 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue, Rh at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR14, -CONR R15, -CO-H, -COR14, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monova- lent 5 to 14 membered aromatic heterocyclic residue;
R' at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR14, -CONR R15, -CO-H, -COR14, Ci-10-alkyl,
C2-io-alkenyl, C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R14 and R15 at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl,
C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic hetero- cyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
R16 and R17 are independently from each other H, Ci-30-alkyl, -CN or halogen.
9. A polymer of any of claims 1 to 7, wherein
L is bivalent 5 to 14 membered aromatic heterocyclic residue optionally substituted with 1 to 4 substituents Rb, wherein
Rb at each occurrence are independently from each other Ci-30-alkyl optionally substituted with 1 to 4 substituents Rh, wherein
Rh at each occurrence are independently from each other selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-10-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR14R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR 4, -CONR R15, -CO-H, -COR14, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue.
10. A polymer of any of claims 1 to 7, wherein
L is bivalent 5 to 14 membered aromatic heterocyclic residue, wherein L is substituted with 1 to 2 substituents Rb, wherein
Rb at each occurrence are independently from each other C6-2o-alkyl.
1 1 . A polymer of any of claims 1 to 10, wherein
q and s are independently from each other 1 , 2 or 3,
r is 1 or 2,
and
n is an integer from 5 to 10Ό00.
12. A polymer of claim 1 1 , wherein
q and s are both 1 ,
r is 1 ,
and
n is an integer from 5 to 10Ό00.
13. A polymer of claim 1 , wherein the unit of formula (1 ) is a unit of formula
wherein R1, R2, Ra, L and n are as defined in claim 1 .
14. A polymer of claim 13, wherein L is
15. A polymer of any of claims 1 to 14, wherein n is an integer from 5 to 5Ό00, preferably from 5 to 1 Ό00, more preferably from 5 to 100, and most preferably from 10 to 100.
16. An electronic device comprising the polymer of any of claims 1 to 15.
17. The electronic device of claim 16, wherein the electronic device is an organic field effect transistor (OFET).
18. The electronic device of claim 16, wherein the electronic device is an organic photovoltaic device (OPV).
19. Use of the polymer of any of claims 1 to 15 as semiconducting material.
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| JP2015023190A (en) * | 2013-07-19 | 2015-02-02 | 富士フイルム株式会社 | Organic thin film transistor, organic semiconductor thin film, and organic semiconductor material |
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| WO2018169256A2 (en) * | 2017-03-16 | 2018-09-20 | 서울대학교산학협력단 | Polymer, organic solar cell comprising polymer, perovskite solar cell comprising polymer |
| KR102024826B1 (en) * | 2018-02-19 | 2019-09-24 | 서울대학교산학협력단 | polymer using photo-active layer of organic solar cell and organic solar cell comprising thereof |
| US11387413B2 (en) | 2017-03-16 | 2022-07-12 | Seoul National University R&Db Foundation | Polymer, organic solar cell comprising polymer, perovskite solar cell comprising polymer |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013182262A1 (en) * | 2012-06-04 | 2013-12-12 | Merck Patent Gmbh | Organic semiconductors |
| JP2015023190A (en) * | 2013-07-19 | 2015-02-02 | 富士フイルム株式会社 | Organic thin film transistor, organic semiconductor thin film, and organic semiconductor material |
| JP2015023188A (en) * | 2013-07-19 | 2015-02-02 | 富士フイルム株式会社 | Organic thin film transistor, organic semiconductor thin film, and organic semiconductor material |
Also Published As
| Publication number | Publication date |
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| KR20140018349A (en) | 2014-02-12 |
| CN103492452B (en) | 2016-01-20 |
| EP2702086B1 (en) | 2015-03-18 |
| TW201247739A (en) | 2012-12-01 |
| KR101486694B1 (en) | 2015-01-26 |
| TWI544000B (en) | 2016-08-01 |
| JP2014514414A (en) | 2014-06-19 |
| CN103492452A (en) | 2014-01-01 |
| EP2702086A1 (en) | 2014-03-05 |
| JP5777802B2 (en) | 2015-09-09 |
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