EP2702085A1 - Semiconductor materials based on dithienopyridone copolymers - Google Patents

Semiconductor materials based on dithienopyridone copolymers

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Publication number
EP2702085A1
EP2702085A1 EP12714013.5A EP12714013A EP2702085A1 EP 2702085 A1 EP2702085 A1 EP 2702085A1 EP 12714013 A EP12714013 A EP 12714013A EP 2702085 A1 EP2702085 A1 EP 2702085A1
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EP
European Patent Office
Prior art keywords
alkyl
monovalent
cor
heterocyclic residue
substituents
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP12714013.5A
Other languages
German (de)
French (fr)
Inventor
Ashok Kumar Mishra
Subramanian Vaidyanathan
Hiroyoshi Noguchi
Florian DÖTZ
Yucui GUAN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Priority to EP12714013.5A priority Critical patent/EP2702085A1/en
Publication of EP2702085A1 publication Critical patent/EP2702085A1/en
Withdrawn legal-status Critical Current

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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.
  • OFETs organic field effect transistors
  • OFET organic field-effect transistor
  • OFET organic field-effect transistor
  • R 1 -octylnonyl
  • R n-decyl or n-dodecyl
  • R n-decyl or n-dodecyl for use in organic field-effect transistor (OFET).
  • Monomeric dithienopyridone is also known in the art.
  • the semiconducting material of the present invention is a polymer comprising a unit of formula
  • R 4 is H, Ci-3o-alkyl optionally substituted with 1 to 6 substituents R f , C 2 -3o-alkenyl optionally substituted with 1 to 6 substituents R f , C 2 -3o-alkynyl optionally substituted with 1 to 6 substituents R f , C3-io-cycloalkyl optionally substituted with 1 to 6 substituents Ra, Cs-io-cyclo- alkenyl optionally substituted with 1 to 6 substituents Ra, monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents Ra, C6-i4-aryl optionally substituted with 1 to 6 substituents R h or monovalent 5 to14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R h , wherein
  • R 8 and R 9 at each occurrence are independently from each other selected from the group consisting of Ci- 3 o-alkyl, C 2 - 3 o-alkenyl, C 2 - 3 o-alkynyl, C 3 -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 18 and R 19 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- 3 o-alkyl, C 2 - 3 o-alkenyl, C 2 - 3 o-alkynyl, C 3 -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,
  • 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 formula and/or a unit of formula
  • R 1 is H, Ci-3o-alkyl optionally substituted with 1 to 6 substituents R c , C 2 -3o-alkenyl optionally sub- stituted with 1 to 6 substituents R c , C 2 -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 resi- due optionally substituted with 1 to 6 substituents R e , wherein
  • R 4 is H, Ci-3o-alkyl optionally substituted with 1 to 6 substituents R f , C2-3o-alkenyl optionally substituted with 1 to 6 substituents R f , C2-3o-alkynyl optionally substituted with 1 to 6 sub- stituents R f , C3-io-cycloalkyl optionally substituted with 1 to 6 substituents Ra, Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents Rs, monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents Ra, C6-i4-aryl optionally substituted with 1 to 6 substituents R h or monovalent 5 to14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents R h , wherein
  • 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,
  • G 1 and G 2 are independently from each other
  • R 18 and R 19 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 16 and R 17 are independently from each other H, Ci- 3 o-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 "essentially consisting of means that at least 80% by weight, more preferably at least 90% by weight, of the polymer consists of the sum of units of formula (1 ) and (1 ') based on the weight of the polymer. More preferably, the semiconducting material of the present invention is a polymer consisting of a unit of formula
  • R 1 is H, Ci-3o-alkyl optionally substituted with 1 to 6 substituents R c , C 2 -3o-alkenyl optionally substituted with 1 to 6 substituents R c , C 2 -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 het- erocyclic 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
  • X is N or C-R 4 , wherein
  • R 5 and R 6 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, C 3 -io-cycloalkyl, Cs-io-cycloalkenyl and monovalent 3 to 14 membered aliphatic heterocyclic residue, wherein R 5 and R 6 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, C 3 -io-cycloalkyl,
  • 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 8 and R 9 at each occurrence are independently from each other selected from the group consisting of Ci- 3 o-alkyl, C 2 - 3 o-alkenyl, C 2 - 3 o-alkynyl, C 3 -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 10 and R 11 at each occurrence are independently from each other se- lected from the group consisting of Ci-10-alkyl, C 2 -io-alkenyl, C 2 -io-alkynyl,
  • G 1 and G 2 are independently from each other
  • R 18 and R 19 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-cyclo- alkenyl, 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-io-alkyl and Ci-30-alkyl can be branched or unbranched.
  • Examples of Ci-10-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, ferf-butyl, n-pentyl, neopentyl, isopentyl, n-(1 -ethyl)propyl, n-hexyl, n-heptyl, n-octyl, n-(2-ethyl)hexyl, n-nonyl and n-decyl.
  • Ci-3o-alkyl examples are Ci-10-alkyl, and n-undecyl, n-dodecyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetra- decyl, 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 (C28) and n-triacontyl (C30).
  • 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.
  • C2-3o-alkenyl examples include C2-io-alkenyl, and linoleyl (Cie), linolenyl (Cie), oleyl (Cie), 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 hetero- cyclic residues containing two heteroatoms such as imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, oxazolidinyl, oxazolinyl, isoxazolidinyl, isoxazolinyl, thiazolidinyl, thiazolinyl, isothia- zolidinyl
  • 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 monovalent 7 to 12 membered, tricyclic monovalent 9 to 14 membered aromatic heterocyclic residue, or tetracyclic monovalent 9 to 14 membered aromatic heterocyclic residues.
  • monocyclic monovalent 5 to 8 membered aromatic heterocyclic residues are monocyclic 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 s membered aromatic heterocyclic residues containing three heteroatoms such as 1 ,2,3-triazolyl, 1 ,2,4-triazolyl and oxadiazolyl, monocyclic monovalent 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
  • bicyclic monovalent 7 membered aromatic heterocyclic residues containing one heteroatom such as azepinyl
  • monocyclic monovalent 7 membered aromatic heterocyclic residues containing two heteroatoms such as 1 ,2-diazepinyl
  • 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 residue
  • bicyclic monovalent 10 membered aromatic heterocyclic residues containing three heteroatoms such as pyridopyrazinyl, pyridopyrimidinyl and pyridopyridazinyl
  • bicyclic monovalent 10 membered aromatic heterocyclic residues containing four heteroatoms such as pteridinyl.
  • 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, ferf-butoxy, n-pentoxy, neopentoxy, isopentoxy, hexoxy, n-heptoxy, n-octoxy, n-nonoxy and n-decoxy.
  • Ci-30-alkoxy examples 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.
  • C6-i4-arylene examples include monocyclic C6-arylene such as phenylene, bicyclic Cg-io-arylene such as naphthylene, for example indenylene, for example
  • Ci2-i4-arylene such as anthrylene
  • fluorenylene for example and
  • C6-24-arylene examples include C6-i4-arylene and pyrenylene, for example
  • perylenylene 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 monocyc- lie 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 pyhdylene, monocyclic bivalent 6 membered aromatic aromatic
  • 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, for example
  • 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 examples are the following compounds
  • An example of a tricyclic bivalent 9 to 14 membered aromatic heterocyclic residue containing heteroatoms is the following compound
  • 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:
  • R 1 is H, Ci-3o-alkyl optionally substituted with 1 to 6 substituents R c , C 2 -3o-alkenyl optionally sub- stituted with 1 to 6 substituents R c , C 2 -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 or monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents R d , wherein
  • R 2 and R 3 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,
  • X is C-R 4 , wherein
  • R 5 and R 6 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,
  • 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 8 and R 9 at each occurrence are independently from each other selected from the group consisting of Ci- 3 o-alkyl, C 2 - 3 o-alkenyl, C 2 - 3 o-alkynyl, C 3 -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 wherein
  • R 18 and R 19 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- 3 o-alkyl, C 2 - 3 o-alkenyl, C 2 - 3 o-alkynyl, C 3 -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,
  • R 16 and R 17 are independently from each other H or Ci-30-alkyl
  • 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 5 to 10 ⁇ 00.
  • R 1 is H or Ci-30-alkyl optionally substituted with 1 to 6 substituents R c , wherein
  • X is C-R 4 , wherein
  • R 4 is H or Ci-30-alkyl optionally substituted with 1 to 6 substituents R f , wherein
  • 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
  • G 1 and G 2 are independently from each other
  • R 18 and R 19 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- 3 o-alkyl, C 2 - 3 o-alkenyl, C 2 - 3 o-alkynyl, C 3 -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,
  • R 16 and R 17 are independently from each other H or Ci-30-alkyl, 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 5 to 10 ⁇ 00.
  • X is C-R 4 , wherein
  • 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 8 and R 9 at each occurrence are independently from each other selected from the group consisting of Ci- 3 o-alkyl, C 2 - 3 o-alkenyl, C 2 - 3 o-alkynyl, C 3 -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,
  • L is monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue optionally substituted with 1 to 4 substituents R b , wherein
  • R 12 and R 13 at each occurrence are independently from each other selected from the group consisting of Ci- 3 o-alkyl, C2- 3 o-alkenyl, C2- 3 o-alkynyl, C 3 -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 or Ci-30-alkyl
  • 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 5 to 10 ⁇ 00.
  • R 1 is Ci-M-alkyl
  • X is C-R 4 , wherein
  • R 4 is H
  • 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
  • L is monocyclic bivalent 5 to 8 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
  • R 16 and R 17 are both H, q and s are both 1 , r is 1 , and n is an integer from 5 to 10 ⁇ 00.
  • a particular preferred unit of formula (1 ) is the unit of formula
  • R 1 , X, R a , L and n are as defined above.
  • a particular preferred unit of formula (V) is the unit of formula
  • R 1 , X, R a , L and n are as defined above.
  • n is an integer from 5 to 5 ⁇ 00, more preferably from 5 to 1 '000, even more bly from 5 to 100, and most preferably from 10 to 100.
  • n is an integer from 10 to 1000, preferably from 10 to 100, and wherein n is an integer from 10 to 1000, preferably from 10 to 100.
  • n is an integer from 10 to 1000, preferably from 10 to 100.
  • 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 ) and/or (1 '), respectively, (1a) and/or (1 'a) 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 ) and/or (1 '), respectively, (1a) and/or (1 'a).
  • the polymer comprising a unit of formula (1 ) and/or (1 ') can be prepared by methods known in the art.
  • the polymer comprising a unit of formula (1 ) and/or (1 ') can, for example, be prepared by treating a compound of formula
  • R 1 and X are as defined above, and Hal is halogen, preferably -Br, with a compound of formula
  • R 102/ - (G 1 ), ⁇ (G 2 ). - R 102 wherein G 1 , G 2 , L, q, r and s are as defined above, and R 100 , R 101 and R 102 are independently from each other Ci-10-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-o-tolylphosphine.
  • 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-tributylstannylthiophene.
  • 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
  • Transition metal catalyst 2 is preferably copper.
  • the reaction is preferably performed at elevated temperatures such 80 to 150 °C, preferably 100 to 120 °C.
  • the reaction can be performed in an inert organic solvent such as dimethylformamide.
  • the crude product may be worked up by conventional methods, for example by extracting the crude product with an appropriate solvent, for example with diethylether.
  • the compound of formula (4) can be prepared by treating a compound of formula wherein R 1 and X are as defined above, with a halogenating agent
  • the halogenating agent is preferably /V-bromosuccinimide.
  • the reaction is preferably performed at slightly elevated temperatures such 35 to 80 °C, preferably 40 to 60 °C.
  • the reaction can be performed in an organic solvent such chloroform/acetic 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 dichloromethane.
  • the compound of formula (5) can be prepared by reacting a compound of formula
  • R 1 and X are as defined above, with a compound of formula wherein X is as defined above, and LG 1 is a leaving group, preferably -CI, in the presence of a base.
  • the base is preferably a tertiary amine such as triethylamine.
  • the reaction is preferably performed at slightly elevated temperatures such 35 to 80 °C, preferably at 40 to 60 °C.
  • the reac- tion can be performed in an organic solvent such chloroform/acetic 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 dichloromethane.
  • an electronic device comprising the polymer comprising a unit of formula (1 ) and/or (V) as semiconducting material.
  • the electronic device is an organic field effect transistor (OFET), and in particular a thin film transistor (TFT).
  • the electronic device is an organic photovoltaic device (OPV).
  • an organic field effect transistor comprises a dielectric layer, a semiconducting layer and a substrate.
  • an 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
  • TGBC Top-Gate Bottom-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), poly(methyl- methacrylate) (PMMA), poly(4-vinylphenol) (PVP), polyvinyl alcohol) (PVA), anzocyclobutene (BCB), or polyimide (PI).
  • PS polystyrene
  • PMMA poly(methyl- methacrylate)
  • 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).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • the plastic sub- strate 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 (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 semiconducting 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
  • TFTs thin film transistors
  • Also part of the present invention is the use of the polymer comprising the unit of formula (1 ) and/or (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.
  • the crude compound is purified by column chromatography on silica gel with 0-5% ethyl acetate in hexane as eluent to give 3-dodecylaminothiophene (6a) as a brown solid (5.75 g, 49%).
  • 3-thiophenecarboxylic acid (3.50 g, 27.31 mmol) and toluene (80 ml.) are added to a round- bottom-flask.
  • Oxalyl chloride (3.57 ml_, 40.97 mmol) and DMF (1 drop) are then added to the mixture.
  • the reaction mixture is heated at 80 °C overnight.
  • the solvent is removed under vac- uum and the remaining crude solid is dissolved in toluene and dried over calcium hydride followed by evaporation of solvent.
  • 3-thiophenecarbonylchloride (7a) is a brown solid (3.02 g, 75.43%) and is directly used in example 3 without further purification.
  • 3-dodecylaminothiophene (6a) (5.62 g, 21 .01 mmol), THF (40 ml_), and triethylamine (3.87 g, 38.20 mmol) are added to a round-bottom-flask under nitrogen.
  • 3-thiophenecarbonylchloride (7a) (2.80 g, 19.10 mmol) in THF (20 ml.) is then added drop wise.
  • the reaction mixture is then allowed to warm to room temperature and is stirred overnight.
  • the mixture is poured into water and extracted with dichloromethane.
  • the organic layer is dried over Na2S0 4 .
  • N-bromosuccinimide (1 1.31 g, 63.56 mmol) is added, and the reaction mixture is stirred for 2 hours at room temperature followed by stirring at 50 °C. The reaction is monitored by thin layer chromatography. Additional amount of NBS is added till the reaction is completed. Water is added to quench the reaction mixture and the reaction mixture is extracted with dichloro- methane. The organic layer is dried over Na2S0 4 . Crude compound 4a is purified by column chromatography on silica gel with 0-60% dichloromethane in hexane as eluent to give compound 4a as a green liquid. (4.8 g, 42.7%).
  • polymer P1 essentially consisting of the unit of formula 1 b and/or 1 'b is dissolved in chlorobenzene and reprecipitated in methanol.
  • the final polymer P1 essentially consisting of the unit of formula 1 b and/or 1 'b is a brown solid (105 mg).
  • poly- mer P2 essentially consisting of the unit of formula 1 c and/or 1 'c is dissolved in chlorobenzene and reprecipitated in methanol.
  • the final polymer P2 essentially consisting of the unit of formula 1 c and/or 1 'c is a brown solid (150 mg).
  • Top-gate bottom-contact (TGBC) thin film transistors TFTs are fabricated on glass (PGO glass used as received).
  • Au source-drain contacts (30 nm-thick) are thermally-evaporated.
  • the substrates are then coated with the semiconductor layer (thickness: 30 to 40 nm) by spin-coating (1500 rpm) a solution of polymer P1 , respectively, P2 in toluene (concentration ⁇ 10 mg/mL), and drying the film at 90 °C for 30 seconds.
  • a 4 weight% polystyrene solution in isopropylace- tate 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).
  • top-gate, bottom-contact (TGBC) thin film transistors of example 8 show the following mo- bility:

Abstract

The present invention provides a polymer comprising a unit of formula (1) or/and (1') The present invention also provides an electronic device comprising the polymer as semiconducting material.

Description

Semiconductor materials based on dithienopyridone 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 polymeric organic semiconducting materials in electronic devices is known in the art.
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
for use in organic field effect transistors (OFETs).
Xiao, S; Zhou H.; You, W. Macromolecules 2008, 41, 5688-5696 describes the following polymers
and
as donor materials for use in photovoltaic devices.
Scharber, M. C; Koppe, M.; Gao, J.; Cordelia, F.; Loi, M. A.; Denk, P.; Morana, M.; Egelhaaf, H.-J.; Forberich, K.; Dennler, G.; Gaudiana, R.; Waller, D.; Zhu, Z.; Shi, X.; Brabec, C. J. Adv. Mater. 2009, 21, 1 -4 describes the following polymers
as donor materials for use in solar cells. Rieger, R.; Beckmann, D.; Pisula, W.; Steffen, W.; Kastler, M.; Mullen K. Adv. Mater. 2010, 22, 83-86 describes the following polymers
for use in organic field-effect transistor (OFET).
Junying Liu, Rui Zhang, Genevieve Sauve, Tomasz Kowalewski, Richard D. McCullough, J. Am. Chem. Soc. 2008, 130, 13167-13176 describes the polymers
for use in organic field-effect transistor (OFET).
Xugang Guo, Rocio P. Ortiz, Yan Zheng, Yan Hu, Yong-Young Noh, Kang-Jun Baeg, Antonio Facchetti, Tobin J. Marks, J. Am. Chem. Soc. 2011 , 133, 1405-1418 describes the polymers
R= 1 -octylnonyl R = n-decyl or n-dodecyl
R = n-decyl or n-dodecyl for use in organic field-effect transistor (OFET).
Monomeric dithienopyridone is also known in the art.
G. J. Heeres and H. Wynberg, Synth. Comm. 1971 , 1, 29 to 31 report the synthesis of dithieno- pyridone monomer of formula
It was the object of the present invention to provide new polymeric semiconducting materials. This object is solved by the polymer of claim 1 and the electronic device of claim 15.
The semiconducting material of the present invention is a polymer comprising a unit of formula
and/or wherein R1 is H , Ci-3o-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 substi- tuted 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-i0-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR2, -S-Ci-10-alkyl, -N H2, -N H R2, -N R2R3, -N H-COR2, -COOH , -COOR2, -CON H2, -CO N H R2, -CON R2R3, -CO-H , -COR2, C3-i0-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-i0-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR2, -S-Ci-10-alkyl, -N H2, -N H R2, -N R2R3, -N H-COR2, -COOH , -COOR2, -CON H2, -CO N H R2, -CON R2R3, -CO-H , -COR2, Ci-i0-alkyl, C2-i0-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-i0-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR2, -S-Ci-10-alkyl, -N H2, -N H R2, -N R2R3, -N H-COR2, -COOH , -COOR2, -CON H2, -CO N H R2, -CON R2R3, -CO-H , -COR2, Ci-i0-alkyl, C2-i0-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl and monovalent s to 14 membered aliphatic heterocyclic residue, wherein R2 and R3 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 s to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue, X is N or C-R4, wherein
R4 is H, Ci-3o-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 Ra, Cs-io-cyclo- alkenyl optionally substituted with 1 to 6 substituents Ra, monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents Ra, C6-i4-aryl optionally substituted with 1 to 6 substituents Rh or monovalent 5 to14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Rh, 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-i0-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR5, -S-Ci-10-alkyl, -NH2, -NHR5, -NR5R6, -NH-COR5, -COOH, -COOR5, -CONH2, -CO NHR5, -CONR5R6, -CO-H, -COR5, 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-i0-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR5, -S-Ci-10-alkyl, -NH2, -NHR5, -NR5R6, -NH-COR5, -COOH, -COOR5, -CONH2, -CO NHR5, -CONR5R6, -CO-H, -COR5, Ci-i0-alkyl,
C2-io-alkenyl, C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 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-i0-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR5, -S-Ci-10-alkyl, -NH2, -NHR5, -NR5R6, -NH-COR5, -COOH, -COOR5, -CONH2, -CO NHR5, -CONR5R6, -CO-H, -COR5, Ci-i0-alkyl,
C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl and monovalent 3 to 14 membered aliphatic heterocyclic residue, wherein R5 and R6 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 s to14 membered aliphatic heterocyclic residue, C6-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, -O-CH2CH2O-Ci-30-alkyl, -O-COR8, -S-Ci-30-alkyl, -N H2, -N H R8, -N R8R9, -N H-COR8, -COOH , -COOR8, -CON H2, -CO N H R8, -CON R8R9, -CO-H , -COR8, Ci-30-alkyl optionally substituted with 1 to 6 substituents R, C2-3o-alkenyl optionally substituted with 1 to 6 substituents R, C2-3o-alkynyl optionally substituted with 1 to 6 substituents R, C3-io-cycloalkyl 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
R8 and R9 at each occurrence are independently from each other selected from the group consisting of Ci-3o-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,
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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR10, -S-Ci-10-alkyl, -N H2, -N H R10, -N R10R11 , -N H-COR10 -COOH , -COOR10, -CON H2, -CON H R10, -CON R10R11 , -CO-H , -COR10, C3-i0-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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR10, -S-Ci-10-alkyl, -N H2, -N H R10, -N R10R11 , -N H-COR10 -COOH , -COOR10, -CON H2, -CON H R10, -CON R10R11 , -CO-H , -COR10, Ci-i0-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
wherein
R18 and R19 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, -N H2, -N H R12, -N R12R13, -N H-COR12, -COOH , -COOR12, -CON H2, -CON H R12, -CON R12R13, -CO-H , -COR12, Ci-30-alkyl option- ally substituted with 1 to 6 substituents Rk, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rk, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rk, 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-3o-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,
Rk 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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR14, -S-Ci-10-alkyl, -N H2, -N H R14, -N R14R15, -N H-COR14,
-COOH , -COOR14, -CON H2, -CON H R14, -CON R1 R15, -CO-H , -COR14, C3-i0-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; R1 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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR14, -S-Ci-10-alkyl, -N H2, -N H R14, -N R14R15, -N H-COR14, -COOH , -COOR14, -CON H2, -CON H R14, -CON R1 R15, -CO-H , -COR14, Ci-i0-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 lected 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,
wherein
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 formula and/or a unit of formula
wherein
R1 is H, Ci-3o-alkyl optionally substituted with 1 to 6 substituents Rc, C2-3o-alkenyl optionally sub- stituted 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 resi- due 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-i0-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR2, -S-Ci-10-alkyl, -NH2, -NHR2, -NR2R3, -NH-COR2, -COOH, -COOR2, -CONH2, -CO NHR2, -CONR2R3, -CO-H, -COR2, C3-i0-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-i0-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR2, -S-Ci-10-alkyl, -NH2, -NHR2, -NR2R3, -NH-COR2, -COOH, -COOR2, -CONH2, -CO NHR2, -CONR2R3, -CO-H, -COR2, Ci-i0-alkyl, C2-i0-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-i0-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -O-COR2, -S-Ci-10-alkyl, -NH2, -NHR2, -NR2R3, -NH-COR2, -COOH, -COOR2, -CON H2, -CON H R2, -CON R2R3, -CO-H, -COR2, Ci-io-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl and monovalent s to 14 membered aliphatic heterocyclic residue, wherein R2 and R3 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, X is N or C-R4, wherein
R4 is H, Ci-3o-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 sub- stituents Rf, C3-io-cycloalkyl optionally substituted with 1 to 6 substituents Ra, Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents Rs, monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents Ra, C6-i4-aryl optionally substituted with 1 to 6 substituents Rh or monovalent 5 to14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Rh, 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-io-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR5, -S-Ci-io-alkyl, -NH2, -NHR5, -NR5R6, -NH-COR5,
-COOH, -COOR5, -CON H2, -CO NHR5, -CONR5R6, -CO-H, -COR5, C3-i0-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, -NO2, -OH, Ci-io-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR5, -S-Ci-io-alkyl, -NH2, -NHR5, -NR5R6, -NH-COR5, -COOH, -COOR5, -CON H2, -CO NHR5, -CONR5R6, -CO-H, -COR5, Ci-io-alkyl, C2-io-alkenyl, C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 membered aromatic hetero- cyclic 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-io-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR5, -S-Ci-10-alkyl, -NH2, -NHR5, -NR5R6, -NH-COR5, -COOH, -COOR5, -CON H2, -CO NHR5, -CONR5R6, -CO-H, -COR5, Ci-10-alkyl,
C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl and monovalent s to 14 membered aliphatic heterocyclic residue, wherein R5 and R6 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 s to14 membered aliphatic heterocyclic residue, C6-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-30-alkyl, -NH2, -NHR8, -NR8R9, -NH-COR8,
-COOH, -COOR8, -CONH2, -CO NHR8, -CONR8R9, -CO-H, -COR8, Ci-30-alkyl optionally substituted with 1 to 6 substituents R, C2-3o-alkenyl optionally substituted with 1 to 6 substituents R, C2-3o-alkynyl optionally substituted with 1 to 6 substituents R, C3-io-cycloalkyl 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 R8 and R9 at each occurrence are independently from each other selected from the group consisting of Ci-3o-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, 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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR10R11, -NH-COR10, -COOH, -COOR10, -CONH2, -CONHR10, -CONR10R11, -CO-H, -COR10, C3-i0-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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR10R11, -NH-COR10, -COOH, -COOR10, -CONH2, -CONHR10, -CONR10R11, -CO-H, -COR10, Ci-i0-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,
G1 and G2 are independently from each other
wherein
R18 and R19 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, -NR12R13, -NH-COR12,
-COOH, -COOR12, -CONH2, -CONHR12, -CONR12R13, -CO-H, -COR12, Ci-30-alkyl optionally substituted with 1 to 6 substituents Rk, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rk, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rk, 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-3o-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, Rk 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-io-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR14, -S-Ci-io-alkyl, -NH2, -NHR14, -NR14R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR14, -CONR1 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-io-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR14, -S-Ci-io-alkyl, -NH2, -NHR14, -NR14R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR14, -CONR1 R15, -CO-H, -COR14, Ci-io-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
wherein
R16 and R17 are independently from each other H, Ci-3o-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 "essentially consisting of means that at least 80% by weight, more preferably at least 90% by weight, of the polymer consists of the sum of units of formula (1 ) and (1 ') based on the weight of the polymer. More preferably, the semiconducting material of the present invention is a polymer consisting of a unit of formula
wherein
R1 is H, Ci-3o-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 het- erocyclic 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-i0-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR2, -S-Ci-10-alkyl, -NH2, -NHR2, -NR2R3, -NH-COR2, -COOH, -COOR2, -CONH2, -CO NHR2, -CONR2R3, -CO-H, -COR2, C3-i0-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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR2, -S-Ci-io-alkyl, -N H2, -N H R2, -N R2R3, -N H-COR2, -COOH , -COOR2, -CON H2, -CO N H R2, -CON R2R3, -CO-H , -COR2, Ci-io-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-io-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR2, -S-Ci-io-alkyl, -N H2, -N H R2, -N R2R3, -N H-COR2, -COOH , -COOR2, -CON H2, -CO N H R2, -CON R2R3, -CO-H , -COR2, Ci-io-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl and monovalent s to 14 membered aliphatic heterocyclic residue, wherein R2 and R3 at each occurrence are independently from each other selected from the group consisting of Ci-io-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, monovalent s to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue,
X is N or C-R4, wherein
R4 is H , Ci-30-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 Ra, Cs-io-cycloalkenyl optionally substituted with 1 to 6 substituents Rs, monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents Ra, C6-i4-aryl optionally substituted with 1 to 6 substituents Rh or monovalent 5 to14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Rh, 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-io-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR5, -S-Ci-10-alkyl, -N H2, -N H R5, -N R5R6, -N H-COR5, -COOH , -COOR5, -CON H2, -CO N H R5, -CON R5R6, -CO-H , -COR5, 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-io-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR5, -S-Ci-10-alkyl, -N H2, -N H R5, -N R5R6, -N H-COR5, -COOH , -COOR5, -CON H2, -CO N H R5, -CON R5R6, -CO-H , -COR5, Ci-10-alkyl,
C2-io-alkenyl, C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 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-io-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR5, -S-Ci-io-alkyl, -NH2, -NHR5, -NR5R6, -NH-COR5, -COOH, -COOR5, -CONH2, -CO NHR5, -CONR5R6, -CO-H, -COR5, Ci-io-alkyl,
C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl and monovalent 3 to 14 membered aliphatic heterocyclic residue, wherein R5 and R6 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 s to14 membered aliphatic heterocyclic residue, C6-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,
-O-CH2CH2O-Ci-30-alkyl, -O-COR8, -S-Ci-30-alkyl, -NH2, -NHR8, -NR8R9, -NH-COR8, -COOH, -COOR8, -CONH2, -CO NHR8, -CONR8R9, -CO-H, -COR8, Ci-30-alkyl optionally substituted with 1 to 6 substituents R, C2-3o-alkenyl optionally substituted with 1 to 6 sub- stituents R, C2-3o-alkynyl optionally substituted with 1 to 6 substituents R, C3-io-cycloalkyl 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
R8 and R9 at each occurrence are independently from each other selected from the group consisting of Ci-3o-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 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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR10R11, -NH-COR10, -COOH, -COOR10, -CONH2, -CONHR10, -CONR10R11, -CO-H, -COR10, C3-i0-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; Ri 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-io-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR10, -S-Ci-io-alkyl, -NH2, -NHR10, -NR10R11, -NH-COR10, -COOH, -COOR10, -CONH2, -CONHR10, -CONR10R11, -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 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,
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
wherein
R18 and R19 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,
-O-CH2CH2O-Ci-30-alkyl, -O-COR12, -S-Ci-30-alkyl, -NH2, -NHR12, -NR12R13, -NH-COR12, -COOH, -COOR12, -CONH2, -CONHR12, -CONR12R13, -CO-H, -COR12, Ci-30-alkyl optionally substituted with 1 to 6 substituents Rk, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rk, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rk, 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-cyclo- alkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
Rk 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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR14R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR14, -CONR1 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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR14R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR14, -CONR1 R15, -CO-H, -COR14, Ci-i0-alkyl, C2-io-alkenyl, C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 membered aromatic het- erocyclic residue; wherein R14 and R15 at each occurrence are independently from each other lected 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.
Ci-io-alkyl and Ci-30-alkyl can be branched or unbranched. Examples of Ci-10-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, ferf-butyl, n-pentyl, neopentyl, isopentyl, n-(1 -ethyl)propyl, n-hexyl, n-heptyl, n-octyl, n-(2-ethyl)hexyl, n-nonyl and n-decyl. Examples of Ci-3o-alkyl are Ci-10-alkyl, and n-undecyl, n-dodecyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetra- decyl, 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 (C28) and n-triacontyl (C30). 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 (Cie), linolenyl (Cie), oleyl (Cie), 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 hetero- cyclic 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, mono- cyclic 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 monovalent 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 monocyclic 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 s membered aromatic heterocyclic residues containing three heteroatoms such as 1 ,2,3-triazolyl, 1 ,2,4-triazolyl and oxadiazolyl, monocyclic monovalent 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, benzoxazolyl, benzisooxazolyl, benzthiazolyl, benzisothiazolyl, furopyridyl and thienopyridyl, bicyclic monovalent 9 membered aromatic heterocyclic residues containing three heteroatoms such as benzotriazolyl, benzoxadiazolyl, oxazolopyridyl, isooxazolopyridyl, thiazolopyridyl, isothiazolopyridyl 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, ferf-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
perylenylene, for example
indenofluorenylene, for example
pentacenylene, for example
*
coronenylene, 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 monocyc- lie 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 pyhdylene, 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
benzofurylene, isobenzofurylene, benzothiophenylene and isobenzothiophenylene, bicyclic bivalent 9 membered aromatic heterocyclic residues containing two heteroatoms such as indazolylene, benzimidazolylene, benzimidazolinylene, benzoxazolylene, benzisooxa- zolylene, benzthiazolylene, benzisothiazolylene, furopyridylene and thienopyridylene, bicyclic bivalent 9 membered aromatic heterocyclic residues containing three heteroatoms such as benzotriazolylene, benzoxadiazolylene, oxazolopyridylene, isooxazolopyridylene, thia- zolopyridylene, isothiazolopyridylene, imidazopyridylene, benzothiadiazolylene, for example *
*
and dioxanothiophenylene, 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, for example
* quinazolinylene, cinnolinylene, phthalazinylene, 1 ,5-naphthyridinylene and
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
and dibenzopyrrolylene, 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
An example of a tetracyclic bivalent 9 to 14 membered aromatic heterocyclic residue containing four 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 ) and (1 ")
R1 is H, Ci-3o-alkyl optionally substituted with 1 to 6 substituents Rc, C2-3o-alkenyl optionally sub- stituted 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 or monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents Rd, 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-io-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR2, -S-Ci-io-alkyl, -NH2, -NHR2, -NR2R3, -NH-COR2, -COOH, -COOR2, -CONH2, -CO NHR2, -CONR2R3, -CO-H, -COR2, 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-io-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -O-COR2, -S-Ci-io-alkyl, -NH2, -NHR2, -NR2R3, -NH-COR2, -COOH, -COOR2, -CONH2, -CONHR2, -CON R2R3, -CO-H, -COR2, Ci-io-alkyl, C2-io-alkenyl,
C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R2 and R3 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 s to 14 membered aliphatic heterocyclic residue,
C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue,
X is C-R4, wherein
R4 is H, Ci-3o-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 Ra, Cs-io-cyclo- alkenyl optionally substituted with 1 to 6 substituents Ra or monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents Ra, 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-io-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR5, -S-Ci-io-alkyl, -NH2, -NHR5, -NR5R6, -NH-COR5, -COOH, -COOR5, -CONH2, -CO NHR5, -CONR5R6, -CO-H, -COR5, C3-i0-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, -NO2, -OH, Ci-io-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR5, -S-Ci-io-alkyl, -NH2, -NHR5, -NR5R6, -NH-COR5, -COOH, -COOR5, -CONH2, -CO NHR5, -CONR5R6, -CO-H, -COR5, Ci-io-alkyl,
C2-io-alkenyl, C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R5 and R6 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 s to14 membered aliphatic heterocyclic residue, C6-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,
-O-CH2CH2O-Ci-30-alkyl, -O-COR8, -S-Ci-30-alkyl, -NH2, -NHR8, -NR8R9, -NH-COR8,
-COOH, -COOR8, -CONH2, -CO NHR8, -CONR8R9, -CO-H, -COR8, Ci-30-alkyl optionally substituted with 1 to 6 substituents R, C2-3o-alkenyl optionally substituted with 1 to 6 substituents R, C2-3o-alkynyl optionally substituted with 1 to 6 substituents R, C3-io-cycloalkyl 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
R8 and R9 at each occurrence are independently from each other selected from the group consisting of Ci-3o-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,
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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR10R11, -NH-COR10 -COOH, -COOR10, -CONH2, -CONHR10, -CONR10R11, -CO-H, -COR10, C3-i0-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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR10R11, -NH-COR10 -COOH, -COOR10, -CONH2, -CONHR10, -CONR10R11, -CO-H, -COR10, Ci-i0-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 heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue, or
G1 and G2 are independently from each other wherein
R18 and R19 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, -NR12R13, -NH-COR12, -COOH, -COOR12, -CONH2, -CONHR12, -CONR12R13, -CO-H, -COR12, Ci-30-alkyl optionally substituted with 1 to 6 substituents Rk, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rk, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rk, 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-3o-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,
Rk 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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR14R15, -NH-COR14,
-COOH, -COOR14, -CONH2, -CONHR14, -CONR1 R15, -CO-H, -COR14, C3-i0-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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR14R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR14, -CONR1 R15, -CO-H, -COR14, Ci-i0-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, C3-10- cycloalkyl, Cs-io-cycloalkenyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue,
wherein
R16 and R17 are independently from each other H or Ci-30-alkyl,
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 5 to 10Ό00.
In more preferred units of formula (1 ) and (V)
R1 is H or 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, -NO2, -OH, Ci-io-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR2, -S-Ci-io-alkyl, -NH2, -NHR2, -NR2R3, -NH-COR2, -COOH, -COOR2, -CON H2, -CO NHR2, -CONR2R3, -CO-H, -COR2, C3-i0-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R2 and R3 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 s to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue,
X is C-R4, wherein
R4 is H or Ci-30-alkyl optionally substituted with 1 to 6 substituents Rf, wherein
Rf at each occurrence are independently from each other selected from the group consist- ing of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-i0-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR5, -S-Ci-10-alkyl, -NH2, -NHR5, -NR5R6, -NH-COR5, -COOH, -COOR5, -CONH2, -CO NHR5, -CONR5R6, -CO-H, -COR5, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R5 and R6 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 s to14 membered aliphatic heterocyclic residue, C6-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,
-O-CH2CH2O-Ci-30-alkyl, -O-COR8, -S-Ci-30-alkyl, -NH2, -NHR8, -NR8R9, -NH-COR8, -COOH, -COOR8, -CONH2, -CO NHR8, -CONR8R9, -CO-H, -COR8, Ci-30-alkyl optionally substituted with 1 to 6 substituents R, C2-3o-alkenyl optionally substituted with 1 to 6 substituents R, C2-3o-alkynyl optionally substituted with 1 to 6 substituents R, C3-io-cycloalkyl 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 resi- due optionally substituted with 1 to 6 substituents R, 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,
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-i0-alkoxy, -0-CH2CH20-Ci-io-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR10R11, -NH-COR10 -COOH, -COOR10, -CONH2, -CONHR10, -CONR10R11, -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;
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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR10R11, -NH-COR10 -COOH, -COOR10, -CONH2, -CONHR10, -CONR10R11, -CO-H, -COR10, Ci-i0-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 heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue, or
G1 and G2 are independently from each other
R18 and R19 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, -NR12R13, -NH-COR12, -COOH, -COOR12, -CONH2, -CONHR12, -CONR12R13, -CO-H, -COR12, Ci-30-alkyl optionally substituted with 1 to 6 substituents Rk, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rk, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rk, 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-3o-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,
Rk 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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR14R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR14, -CONR1 R15, -CO-H, -COR14, C3-i0-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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR14R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR14, -CONR1 R15, -CO-H, -COR14, Ci-i0-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 wherein
R16 and R17 are independently from each other H or Ci-30-alkyl, 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 5 to 10Ό00.
In even more preferred units of formula (1 ) and (V)
R1 is Ci-3o-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-io-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR2, -S-Ci-io-alkyl, -NH2, -NHR2, -NR2R3, -NH-COR2, -COOH, -COOR2, -CONH2, -CO NHR2, -CONR2R3, -CO-H, -COR2, C3-i0-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R2 and R3 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 s to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue,
X is C-R4, wherein
R4 is H or Ci-3o-alkyl optionally substituted with 1 to 6 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-io-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR5, -S-Ci-io-alkyl, -NH2, -NHR5, -NR5R6, -NH-COR5, -COOH, -COOR5, -CONH2, -CO NHR5, -CONR5R6, -CO-H, -COR5, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R5 and R6 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 s to14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue,
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 selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-30-alkoxy,
-O-CH2CH2O-Ci-30-alkyl, -O-COR8, -S-Ci-30-alkyl, -NH2, -NHR8, -NR8R9, -NH-COR8, -COOH, -COOR8, -CONH2, -CO NHR8, -CONR8R9, -CO-H, -COR8, Ci-30-alkyl optionally substituted with 1 to 6 substituents R, C2-3o-alkenyl optionally substituted with 1 to 6 substituents R, C2-3o-alkynyl optionally substituted with 1 to 6 substituents R, C3-io-cycloalkyl 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
R8 and R9 at each occurrence are independently from each other selected from the group consisting of Ci-3o-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,
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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR10R11, -NH-COR10, -COOH, -COOR10, -CONH2, -CONHR10, -CONR10R11, -CO-H, -COR10, C3-i0-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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR10, -S-Ci-io-alkyl, -N H2, -N H R10, -N R10R11 , -N H-COR10, -COOH , -COOR10, -CON H2, -CON H R10, -CON R10R11 , -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 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,
L is monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue optionally substituted with 1 to 4 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 , -NO2, -OH , Ci-30-alkoxy,
-0-CH2CH20-Ci-3o-alkyl, -O-COR12, -S-Ci-30-alkyl, -N H2, -N H R12, -N R12R13, -N H-COR12, -COOH , -COOR12, -CON H2, -CON H R12, -CON R12R13, -CO-H , -COR12, Ci-30-alkyl optionally substituted with 1 to 6 substituents Rk, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rk, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rk, 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-3o-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,
Rk 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-i0-alkyl, -O-COR14, -S-Ci-10-alkyl, -N H2, -N H R14, -N R14R15, -N H-COR14, -COOH , -COOR14, -CON H2, -CON H R14, -CON R1 R15, -CO-H , -COR14, C3-i0-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 , -NO2, -OH , Ci-10-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR14, -S-Ci-10-alkyl, -N H2, -N H R14, -N R14R15, -N H-COR14, -COOH, -COOR14, -CONH2, -CONHR14, -CONR14R15, -CO-H, -COR14, Ci-io-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
wherein
R16 and R17 are independently from each other H or Ci-30-alkyl,
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 5 to 10Ό00.
In most preferred units of formula (1 ) and (V)
R1 is Ci-M-alkyl
X is C-R4, wherein
R4 is H, 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,
L is monocyclic bivalent 5 to 8 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
L is
wherein
R16 and R17 are both H, q and s are both 1 , r is 1 , and n is an integer from 5 to 10Ό00.
A particular preferred unit of formula (1 ) is the unit of formula
wherein R1, X, Ra, L and n are as defined above.
A particular preferred unit of formula (V) is the unit of formula
wherein R1, X, Ra, L and n are as defined above.
In particular preferred units of formula (1 a), (1 '), (1a) and (1 'a)
L is
Preferably, n is an integer from 5 to 5Ό00, more preferably from 5 to 1 '000, even more bly from 5 to 100, and most preferably from 10 to 100.
Particular preferred examples of units of formulae (1 ) and (1 a) are the units of formula
wherein n is an integer from 10 to 1000, preferably from 10 to 100, and wherein n is an integer from 10 to 1000, preferably from 10 to 100.
Particular preferred examples of units of formulae (V) and (1 'a) are the units of formula
wherein n is an integer from 10 to 1000, preferably from 10 to 100. 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 ) and/or (1 '), respectively, (1a) and/or (1 'a) based on the weight of the polymer. Most preferably, the semiconducting material of the present invention is a polymer consisting essentially of a unit of formula (1 ) and/or (1 '), respectively, (1a) and/or (1 'a).
The polymer comprising a unit of formula (1 ) and/or (1 ') can be prepared by methods known in the art.
The polymer comprising a unit of formula (1 ) and/or (1 ') can, for example, be prepared by treating a compound of formula
wherein R1 and X are as defined above, and Hal is halogen, preferably -Br, with a compound of formula
R100 R1 00
R1 R I /R 101
R102/ - (G1), ^(G2). - R102 wherein G1, G2, L, q, r and s are as defined above, and R100, R101 and R102 are independently from each other Ci-10-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-o-tolylphosphine. 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-tributylstannylthiophene. 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
wherein R1, X and Hal are as defined above, with transition metal catalyst 2.
Transition metal catalyst 2 is preferably copper. The reaction is preferably performed at elevated temperatures such 80 to 150 °C, preferably 100 to 120 °C. The reaction can be performed in an inert organic solvent such as dimethylformamide. The crude product may be worked up by conventional methods, for example by extracting the crude product with an appropriate solvent, for example with diethylether.
The compound of formula (4) can be prepared by treating a compound of formula wherein R1 and X are as defined above, with a halogenating agent
The halogenating agent is preferably /V-bromosuccinimide. The reaction is preferably performed at slightly elevated temperatures such 35 to 80 °C, preferably 40 to 60 °C. The reaction can be performed in an organic solvent such chloroform/acetic 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 dichloromethane.
The compound of formula (5) can be prepared by reacting a compound of formula
(6)
wherein R1 and X are as defined above, with a compound of formula wherein X is as defined above, and LG1 is a leaving group, preferably -CI, in the presence of a base.
The base is preferably a tertiary amine such as triethylamine. The reaction is preferably performed at slightly elevated temperatures such 35 to 80 °C, preferably at 40 to 60 °C. The reac- tion can be performed in an organic solvent such chloroform/acetic 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 dichloromethane.
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 ) and/or (V) as semiconducting material. Preferably, the electronic device is an organic field effect transistor (OFET), and in particular a thin film transistor (TFT). Preferably, the electronic 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, an 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), poly(methyl- methacrylate) (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 sub- strate 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 semiconducting 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 ) and/or (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
All reagents are purchased from commercial sources and used without further purification unless otherwise noted. Conventional Schlenk techniques are used, and reactions are carried out under N2 unless otherwise noted. NMR spectra are recorded on a Varian 400MR spectrometer (1H, 400 MHz). Polymer molecular weights are determined on Agilent 1200 series with refractive index detector in THF at room temperature versus polystyrene standards.
Example 1
Preparation of 3-dodecylaminothiophene (6a)
6a
A mixture of 3-bromothiophene (7.20 g, 44.16 mmol), dodecylamine (12.28 g, 166.24 mmol), Cu (0.14 g, 2.21 mmol), Cul (0.42 g, 2.21 mmol), K3PO4 (18.75 g, 88.32 mmol), and N,N-dimethyl- ethanolamine (60 ml.) is purged with N2. The reaction mixture is then stirred for 2 days at 90 °C under nitrogen. The reaction mixture is quenched with water and extracted with diethyl ether followed by washing with brine. The organic layer is dried over Na2S04. The crude compound is purified by column chromatography on silica gel with 0-5% ethyl acetate in hexane as eluent to give 3-dodecylaminothiophene (6a) as a brown solid (5.75 g, 49%). 1H-NMR (400 MHz) ppm 7.1 1 (dd, 1 H, J=3.0Hz, J=5.2Hz), 6.58 (dd, 1 H, J=1 .5Hz, J=5.1 Hz), 5.88 (dd, 1 H, J=1 .5Hz, J=3.0Hz), 3.02 (t, 2H, J=7.1 Hz), 1.58 (m, 2H), 1 .35 (m, 18H), 0.86 (t, 3H, J=6.8Hz).
Example 2
Preparation of 3-thiophenecarbonylchloride (7a)
7a 3-thiophenecarboxylic acid (3.50 g, 27.31 mmol) and toluene (80 ml.) are added to a round- bottom-flask. Oxalyl chloride (3.57 ml_, 40.97 mmol) and DMF (1 drop) are then added to the mixture. The reaction mixture is heated at 80 °C overnight. The solvent is removed under vac- uum and the remaining crude solid is dissolved in toluene and dried over calcium hydride followed by evaporation of solvent. 3-thiophenecarbonylchloride (7a) is a brown solid (3.02 g, 75.43%) and is directly used in example 3 without further purification.
Example 3
Preparation of compound 5a
6a 7a 5a
3-dodecylaminothiophene (6a) (5.62 g, 21 .01 mmol), THF (40 ml_), and triethylamine (3.87 g, 38.20 mmol) are added to a round-bottom-flask under nitrogen. At 0 °C, 3-thiophenecarbonylchloride (7a) (2.80 g, 19.10 mmol) in THF (20 ml.) is then added drop wise. The reaction mixture is then allowed to warm to room temperature and is stirred overnight. The mixture is poured into water and extracted with dichloromethane. The organic layer is dried over Na2S04. The crude compound is purified by column chromatography on silica gel with 0-10% ethyl acetate in hexane as eluent to give compound 5a as light brown solid (6.1 g, 84.6%). 1H-NMR (400 MHz) ppm 7.26 (dd, 1 H, J=3.2Hz, J=5.1 Hz), 7.20 (dd, 1 H, J=1 .1 Hz, J=3.0Hz), 7.08 (dd, 1 H, J=3.0Hz, J=5.1 Hz), 6.93 (dd, 1 H , J=1.2Hz, J=3.1 Hz), 6.91 (dd, 1 H, J=1.1 Hz, J=5.1 Hz), 6.85 (dd, 1 H, J=1 .3Hz, J=5.1 Hz), 3.76 (m, 2H), 1.57 (m, 2H), 1.26 (m, 18H), 0.86 (t, 3H, J=6.8Hz).
Example 4
Preparation of compound 4a
Compound 5a (6.0 g, 15.89 mmol) is dissolved in chloroform (150 ml_)/acetic acid (50 ml.) mixture. The flask is wrapped with aluminium foil to protect the reaction mixture from light.
N-bromosuccinimide (1 1.31 g, 63.56 mmol) is added, and the reaction mixture is stirred for 2 hours at room temperature followed by stirring at 50 °C. The reaction is monitored by thin layer chromatography. Additional amount of NBS is added till the reaction is completed. Water is added to quench the reaction mixture and the reaction mixture is extracted with dichloro- methane. The organic layer is dried over Na2S04. Crude compound 4a is purified by column chromatography on silica gel with 0-60% dichloromethane in hexane as eluent to give compound 4a as a green liquid. (4.8 g, 42.7%). 1H-NMR (400 MHz) ppm 6.87 (s, 1 H), 6.67 (s, 1 H), 3.69 (m, 2H), 1 .54 (d, 2H, J=6.5Hz), 1 .28 (m, 18H), 0.86 (t, 3H, J=6.8Hz).
Example 5
Preparation of compound 2a
4a Cu (0.348 g, 5.48 mmol) is added into a round-bottom-flask under N2. Compound 4a (3.80 g, 5.48 mmol) in DMF (260 ml.) is added and the reaction mixture is stirred at 1 10 °C overnight. The reaction is monitored by thin layer chromatography. Additional Cu is added to complete the reaction. The reaction mixture is quenched with water and extracted with diethylether. The organic layer is washed with water and dried over Na2S04. Crude compound 2a is purified by col- umn chromatography on silica gel with 0-70% dichloromethane in hexane as eluent to give compound 2a as brown solid (0.44 g, 15.0%). 1H-NMR (400 MHz) ppm 7.57 (s, 1 H), 7.10 (s, 1 H), 4.13 (m, 2H), 1.69 (td, 2H, J=7.6Hz, J=15.3Hz), 1 .33 (m, 18H), 0.86 (t, 3H, J=6.8Hz).
Example 6
Preparation of polymer P1 essentially consisting of the unit of formula 1 b and/or (1 'b)
P(o-tolyl)3
2a 3a
1 b and/or
1 'b
Compound 3a (0.1 1 g, 0.13 mmol), tris(dibenzylideneacetone)dipalladium(0) (Pd2dba3)
(0.0036 g, 0.004 mmol), and P(o-tolyl)3 (0.0024 g, 0.008 mmol) are added to a round-bottom- flask and purged with N2. Compound 2a (0.07 g, 0.13 mmol) in chlorobenzene (2.5 ml.) is then added and the mixture is stirred at 130 °C. 2-bromothiophene and 2-tributylstannylthiophene are added to endcap the polymer essentially consisting of the unit of formula 1 b and/or 1 'b followed by precipitation in methanol and filtration. After overnight Soxhlet extraction with acetone, polymer P1 essentially consisting of the unit of formula 1 b and/or 1 'b is dissolved in chlorobenzene and reprecipitated in methanol. The final polymer P1 essentially consisting of the unit of formula 1 b and/or 1 'b is a brown solid (105 mg). Mn = 1 .83 χ 104 g/mol, D = 8.6. Elemental analysis (calcd): C, 71.78 (73.36); H, 8.59 (9.07); N, 1 .30 (1.56). Example 7
Preparation of polymer P2 essentially consisting of the unit of formula 1 c and/or 1 'c
P(o-tolyl)3
2a 3b
and/or
Compound 2a (0.10 g, 0.19 mmol), tris(dibenzylideneacetone)dipalladium(0) (Pd2dba3)
(0.0052 g, 0.006 mmol), and P(o-tolyl)3 (0.0034 g, 0.01 1 mmol) are added to a round-bottom- flask and purged with N2. Compound 3b (0.17 g, 0.19 mmol) in chlorobenzene (7 ml.) is then added and the mixture is stirred at 130 °C. 2-bromothiophene and 2-tributylstannylthiophene are added to endcap the polymer essentially consisting of the unit of formula 1 c and/or 1 'c followed by precipitation in methanol and filtration. After overnight Soxhlet extraction with acetone, poly- mer P2 essentially consisting of the unit of formula 1 c and/or 1 'c is dissolved in chlorobenzene and reprecipitated in methanol. The final polymer P2 essentially consisting of the unit of formula 1 c and/or 1 'c is a brown solid (150 mg). Mn = 1 .64 χ 104 g/mol, D = 3.3. Elemental analysis (calcd): C, 70.75 (71.57); H, 7.67 (8.53); N, 1 .43 (1.46).
Example 8
Preparation of top-gate bottom-contact transistors (TGBC) containing the polymer P1 , respectively, P2 as semiconducting material
Top-gate bottom-contact (TGBC) thin film transistors (TFTs) are fabricated on glass (PGO glass used as received). Au source-drain contacts (30 nm-thick) are thermally-evaporated. The substrates are then coated with the semiconductor layer (thickness: 30 to 40 nm) by spin-coating (1500 rpm) a solution of polymer P1 , respectively, P2 in toluene (concentration ~ 10 mg/mL), and drying the film at 90 °C for 30 seconds. A 4 weight% polystyrene solution in isopropylace- tate 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 μιη and 0.5 mm, respectively, to afford W/L = 10.
The top-gate, bottom-contact (TGBC) thin film transistors of example 8 show the following mo- bility:
P1 : mobility = 1.5 χ 10 3 cm2V"1s-1,
P2: mobility = 1.3 χ 10 3 cm2V"1s-1.

Claims

Claims
1 . A polymer comprising a unit of formula
wherein
R1 is H, Ci-3o-alkyl optionally substituted with 1 to 6 substituents Rc, C2-3o-alkenyl optionally sub- stituted 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 resi- due 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-i0-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR2, -S-Ci-10-alkyl, -NH2, -NHR2, -NR2R3, -NH-COR2, -COOH, -COOR2, -CONH2, -CO NHR2, -CONR2R3, -CO-H, -COR2, C3-i0-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-i0-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR2, -S-Ci-10-alkyl, -NH2, -NHR2, -NR2R3, -NH-COR2, -COOH, -COOR2, -CONH2, -CO NHR2, -CONR2R3, -CO-H, -COR2, Ci-i0-alkyl, C2-i0-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-io-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR2, -S-Ci-io-alkyl, -NH2, -NHR2, -NR2R3, -NH-COR2, -COOH, -COOR2, -CONH2, -CO NHR2, -CONR2R3, -CO-H, -COR2, Ci-io-alkyl, C2-io-alkenyl,
C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl and monovalent s to 14 membered aliphatic heterocyclic residue, wherein R2 and R3 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,
X is N or C-R4, wherein
R4 is H, Ci-3o-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 Ra, Cs-io-cyclo- alkenyl optionally substituted with 1 to 6 substituents Rs, monovalent 3 to 14 membered aliphatic heterocyclic residue optionally substituted with 1 to 6 substituents Ra, C6-i4-aryl optionally substituted with 1 to 6 substituents Rh or monovalent 5 to14 membered aromatic heterocyclic residue optionally substituted with 1 to 6 substituents Rh, 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-io-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR5, -S-Ci-io-alkyl, -NH2, -NHR5, -NR5R6, -NH-COR5, -COOH, -COOR5, -CONH2, -CO NHR5, -CONR5R6, -CO-H, -COR5, 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 consist- ing of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-i0-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR5, -S-Ci-10-alkyl, -NH2, -NHR5, -NR5R6, -NH-COR5, -COOH, -COOR5, -CONH2, -CO NHR5, -CONR5R6, -CO-H, -COR5, Ci-io-alkyl,
C2-io-alkenyl, C2-io-alkynyl, C6-i4-aryl and monovalent 5 to 14 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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR5, -S-Ci-io-alkyl, -NH2, -NHR5, -NR5R6, -NH-COR5, -COOH, -COOR5, -CONH2, -CO NHR5, -CONR5R6, -CO-H, -COR5, Ci-io-alkyl,
C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl and monovalent 3 to 14 membered aliphatic heterocyclic residue, wherein R5 and R6 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 s to14 membered aliphatic heterocyclic residue,
C6-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, -NO2, -OH, Ci-30-alkoxy,
-0-CH2CH20-Ci-3o-alkyl, -O-COR8, -S-Ci-30-alkyl, -NH2, -NHR8, -NR8R9, -NH-COR8, -COOH, -COOR8, -CONH2, -CO NHR8, -CONR8R9, -CO-H, -COR8, Ci-30-alkyl optionally substituted with 1 to 6 substituents R, C2-3o-alkenyl optionally substituted with 1 to 6 substituents R, C2-3o-alkynyl optionally substituted with 1 to 6 substituents R, C3-io-cycloalkyl 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 resi- due optionally substituted with 1 to 6 substituents R, wherein
R8 and R9 at each occurrence are independently from each other selected from the group consisting of Ci-3o-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 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-i0-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR10R11, -NH-COR10, -COOH, -COOR10, -CONH2, -CONHR10, -CONR10R11, -CO-H, -COR10, C3-i0-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, -NO2, -OH, Ci-10-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR10, -S-Ci-io-alkyl, -NH2, -NHR10, -NR10R11, -NH-COR10, -COOH, -COOR10, -CON H2, -CONHR10, -CONR10R11, -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 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
wherein
R18 and R19 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, -NO2, -OH, Ci-30-alkoxy, -0-CH2CH20-Ci-3o-alkyl, -O-COR12, -S-Ci-30-alkyl, -NH2, -NHR12, -NR12R13, -NH-COR12, -COOH, -COOR12, -CON H2, -CONHR12, -CONR12R13, -CO-H, -COR12, Ci-30-alkyl option- ally substituted with 1 to 6 substituents Rk, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rk, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rk, 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-3o-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,
Rk 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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR14R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR14, -CONR1 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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR14R15, -NH-COR14, -COOH, -COOR14, -CONH2, -CONHR14, -CONR1 R15, -CO-H, -COR14, Ci-i0-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 lected 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,
wherein
R16 and R17 are independently from each other H, Ci-3o-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 is H or Ci-3o-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-io-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR2, -S-Ci-io-alkyl, -NH2, -NHR2, -NR2R3, -NH-COR2, -COOH, -COOR2, -CONH2, -CO NHR2, -CONR2R3, -CO-H, -COR2, C3-i0-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R2 and R3 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 s to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue,
X is C-R4, wherein
R4 is H or Ci-3o-alkyl optionally substituted with 1 to 6 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-io-alkoxy,
-0-CH2CH20-Ci-io-alkyl, -O-COR5, -S-Ci-io-alkyl, -NH2, -NHR5, -NR5R6, -NH-COR5,
-COOH, -COOR5, -CONH2, -CO NHR5, -CONR5R6, -CO-H, -COR5, C3-i0-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R5 and R6 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 to14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue, and G1, G2, L, q, s, r and n are as defined in claim 1 .
3. The polymer of claim 1 , wherein
R1 is Ci-3o-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-io-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR2, -S-Ci-io-alkyl, -NH2, -NHR2, -NR2R3, -NH-COR2, -COOH, -COOR2, -CONH2, -CO NHR2, -CONR2R3, -CO-H, -COR2, C3-io-cycloalkyl, monovalent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R2 and R3 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 s to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue,
X is C-R4, wherein
R4 is H or Ci-3o-alkyl optionally substituted with 1 to 6 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-io-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR5, -S-Ci-io-alkyl, -NH2, -NHR5, -NR5R6, -NH-COR5, -COOH, -COOR5, -CONH2, -CO NHR5, -CONR5R6, -CO-H, -COR5, C3-i0-cycloalkyl, mono- valent 3 to 14 membered aliphatic heterocyclic residue, C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue; wherein R5 and R6 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 to14 membered aliphatic heterocyclic residue,
C6-i4-aryl and monovalent 5 to 14 membered aromatic heterocyclic residue, and G1, G2, L, q, s, r and n are as defined in claim 1 .
4. The polymer of claim 1 wherein
R1 is Ci-30-alkyl,
X is C-R4, wherein
R4 is H, and G1, G2, L, q, s, r and n are as defined in claim 1 .
5. 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 selected from the group consisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-30-alkoxy,
-O-CH2CH2O-Ci-30-alkyl, -O-COR8, -S-Ci-30-alkyl, -NH2, -NHR8, -NR8R9, -NH-COR8,
-COOH, -COOR8, -CONH2, -CO NHR8, -CONR8R9, -CO-H, -COR8, Ci-30-alkyl optionally substituted with 1 to 6 substituents R, C2-3o-alkenyl optionally substituted with 1 to 6 substituents R, C2-3o-alkynyl optionally substituted with 1 to 6 substituents R, C3-io-cycloalkyl 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
R8 and R9 at each occurrence are independently from each other selected from the group consisting of Ci-3o-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,
R at each occurrence are independently from each other selected from the group con- sisting of =0, =C(CN)2, -0-C2-6-alkylene-0-, halogen, -CN, -N02, -OH, Ci-i0-alkoxy,
-O-CH2CH2O-Ci-i0-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR10R11, -NH-COR10, -COOH, -COOR10, -CONH2, -CONHR10, -CONR10R11, -CO-H, -COR10, C3-i0-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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR10, -S-Ci-10-alkyl, -NH2, -NHR10, -NR10R11, -NH-COR10, -COOH, -COOR10, -CONH2, -CONHR10, -CONR10R11, -CO-H, -COR10, Ci-i0-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 heterocyclic residue, C6-i4-aryl and monovalent 5 to14 membered aromatic heterocyclic residue.
6. The polymer of any of claims 1 to 5, wherein
L is monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue optionally substituted with 1 to 4 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, -NR12R13, -NH-COR12, -COOH, -COOR12, -CONH2, -CONHR12, -CONR12R13, -CO-H, -COR12, Ci-30-alkyl optionally substituted with 1 to 6 substituents Rk, C2-3o-alkenyl optionally substituted with 1 to 6 substituents Rk, C2-3o-alkynyl optionally substituted with 1 to 6 substituents Rk, 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-3o-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,
Rk 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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR14R15, -NH-COR14 -COOH, -COOR14, -CONH2, -CONHR14, -CONR1 R15, -CO-H, -COR14, C3-i0-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-i0-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR14, -S-Ci-10-alkyl, -NH2, -NHR14, -NR14R15, -NH-COR14 -COOH, -COOR14, -CONH2, -CONHR14, -CONR1 R15, -CO-H, -COR14, Ci-i0-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, BASF SE PF 71920
WO 2012/146504 PCT/EP2012/056943
or L is
wherein
R16 and R17 are independently from each other H or Ci-30-alkyl.
7. The polymer of any of claims 1 to 6, 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.
8. The polymer of any of claims 1 to 7, wherein
L is monocyclic bivalent 5 to 8 membered aromatic heterocyclic residue, wherein L can be op- tionally substituted with 1 to 4 substituents Rb, wherein
Rb at each occurrence are independently from each other Ci-30-alkyl,
or L is
wherein
R16 and R17 are both H.
9. The polymer of any of claims 1 to 8, wherein
q and s are both 1 , BASF SE PF 71920
WO 2012/146504 PCT/EP2012/056943
67 r is 1 , and n is an integer from 5 to 10Ό00.
10. The polymer of claim 1 , wherein the unit of formula (1 ) is a unit of formula
wherein
R1, X, Ra, L and n are as defined in claim 1
1 1. The polymer of claim 10, wherein
L is
and R1, X, Ra and n are as defined in claim 1
12. The polymer of claim 10 or claim 1 1 , wherein
R1 and X are as defined in claim 3 and BASF SE PF 71920
WO 2012/146504 PCT/EP2012/056943
68
Ra and n are as defined in claim 1 .
13. The polymer of claim 10 or claim 1 1 , wherein
R1 and X are as defined in claim 4 and
Ra is as defined in claim 7,
and n is as defined in claim 1 .
14. The polymer of any of claims 1 to 13, wherein 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.
15. An electronic device comprising the polymer of any of claims 1 to 14 as semiconducting material.
16. The electronic device of claim 15, wherein the electronic device is an organic field effect transistor (OFET).
17. The electronic device of claim 15, wherein the electronic device is organic photovoltaic device (OPV).
18. Use of the polymer of any of claims 1 to 14 as semiconducting material.
EP12714013.5A 2011-04-27 2012-04-16 Semiconductor materials based on dithienopyridone copolymers Withdrawn EP2702085A1 (en)

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