WO2012146504A1 - Semiconductor materials based on dithienopyridone copolymers - Google Patents

Semiconductor materials based on dithienopyridone copolymers Download PDF

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Publication number
WO2012146504A1
WO2012146504A1 PCT/EP2012/056943 EP2012056943W WO2012146504A1 WO 2012146504 A1 WO2012146504 A1 WO 2012146504A1 EP 2012056943 W EP2012056943 W EP 2012056943W WO 2012146504 A1 WO2012146504 A1 WO 2012146504A1
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alkyl
monovalent
cor
heterocyclic residue
substituents
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PCT/EP2012/056943
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English (en)
French (fr)
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Ashok Kumar Mishra
Subramanian Vaidyanathan
Hiroyoshi Noguchi
Florian DÖTZ
Yucui GUAN
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Basf Se
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Priority to KR1020137031041A priority Critical patent/KR101486693B1/ko
Priority to EP12714013.5A priority patent/EP2702085A1/en
Priority to CN201280018847.1A priority patent/CN103517936A/zh
Priority to JP2014506816A priority patent/JP2014518904A/ja
Publication of WO2012146504A1 publication Critical patent/WO2012146504A1/en

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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:

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021079141A1 (en) 2019-10-24 2021-04-29 Sumitomo Chemical Co., Ltd Photoactive materials
GB2593130A (en) * 2019-10-24 2021-09-22 Sumitomo Chemical Co Photoactive materials

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