WO2015015397A1 - Naphtyridines substituées en tant que molécules acceptrices pour dispositifs électroniques - Google Patents

Naphtyridines substituées en tant que molécules acceptrices pour dispositifs électroniques Download PDF

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WO2015015397A1
WO2015015397A1 PCT/IB2014/063478 IB2014063478W WO2015015397A1 WO 2015015397 A1 WO2015015397 A1 WO 2015015397A1 IB 2014063478 W IB2014063478 W IB 2014063478W WO 2015015397 A1 WO2015015397 A1 WO 2015015397A1
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alkyl
phenyl
group
substituted
substituents independently
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PCT/IB2014/063478
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Claudia TEUSCH
Manuel HAMBURGER
Klaus MÜLLEN
Stefan HÖFLE
Alexander Colsmann
Uli Lemmer
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Karlsruher Institut Für Technologie Lichttechnisches Institut
MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V.
Innovation Lab Gmbh
Basf (China) Company Limited
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Publication of WO2015015397A1 publication Critical patent/WO2015015397A1/fr

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    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium

Definitions

  • the present invention relates to substituted naphthyridines, to a process for the preparation of these substituted naphthyridines, to electronic devices comprising these substituted naphthyridines and to the use of these substituted naphthyridines as semiconducting materials.
  • Substituted naphyridines are suitable as semiconducting materials for use in electronic devices such as organic photovoltaic (OPV) cells, organic field-effect transistors (OFET) and organic light emitting diodes (OLED).
  • OCV organic photovoltaic
  • OFET organic field-effect transistors
  • OLED organic light emitting diodes
  • WO 2006/098121 describes compounds of general formula An-L-Ar 2 , wherein An and Ar 2 , respectively, represent a hydrogen atom or a substituent, and at least one of An and Ar 2 is an aromatic hydrocarbon fused ring or an aromatic heterocyclic fused ring wherein aromatic hydrocarbon rings or aromatic heterocyclic rings are fused, and L represents a linked group connected by a conjugated system containing an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
  • An and Ar 2 respectively, represent a hydrogen atom or a substituent
  • at least one of An and Ar 2 is an aromatic hydrocarbon fused ring or an aromatic heterocyclic fused ring wherein aromatic hydrocarbon rings or aromatic heterocyclic rings are fused
  • L represents a linked group connected by a conjugated system containing an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
  • n and o are independently an integer between 0 and 6
  • m is an integer between 2 and 8.
  • US 2007/0166871 describes compounds of formula (Ai)-(X) n -(A 2 ), wherein X is independently selected from the group consisting of unsubstituted and substituted C6-C3o-aryl groups and a substituted and unsubstituted C2-C2o-heteroaryl groups containing sulfur (S) or selenium (Se), Ai and A 2 are each independently selected from a C 2 -C 2 o-heteroaryl group containing nitrogen (N) or oxygen (O) and wherein n is 2 to 10.
  • X is independently selected from the group consisting of unsubstituted and substituted C6-C3o-aryl groups and a substituted and unsubstituted C2-C2o-heteroaryl groups containing sulfur (S) or selenium (Se)
  • Ai and A 2 are each independently selected from a C 2 -C 2 o-heteroaryl group containing nitrogen (N) or oxygen (O
  • the compounds are used as semiconducting materials in electronic devices.
  • WO 2012/1 1181 1 describes the following p-type semiconductor materials
  • JP 2004-327106 describes compounds of formula
  • R 1 is aryl
  • a and B are hydrogen or of formula
  • A is a five or six-membered ring. It was the object of the present invention to provide new substituted naphthyridine derivatives.
  • the compounds of the present invention are of formula
  • p 1 , 2, 3, 4, 5 or 6
  • n 0, 1 or 2
  • L 1 is selected from the group consisting of
  • R 50 and R 51 are independently from each other H, Ci-20-alkyl, C(0)-Ci-2o-alkyl, Ci-20-alkenyl, C(0)-phenyl, C(O)-O-Ci- 20 -alkyl, C(0)-0-C 2 -io-alkenyl or C(0)-0-phenyl,
  • Ar 1 is at each occurrence a 5 to 9 membered heteroaromatic moiety, which may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-2o-alkyl, O-Ci- 20 -alkyl, C(0)-Ci -2 o-alkyl, C(O)-O-Ci- 20 -alkyl, phenyl, F, CI and Br, wherein Ci- 20 -alkyl, Ci- 20 -alkyl, O-Ci- 20 -alkyl, C(O)-Ci- 20 -alkyl and C(O)-O-Ci- 20 -alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci_ 10 -alkyl, and
  • Ar 2 is at each occurrence a 5 to 14 membered heteroaromatic moiety or a C6-i4-aromatic moiety, wherein the 5 to 14 membered heteroaromatic moiety and the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci- 2 o-alkyl, C(0)-0-Ci- 2 o-alkyl, phenyl, F, CI and Br,
  • Ci- 20 -alkyl, Ci- 20 -alkyl, O-Ci- 20 -alkyl, C(0)-Ci- 2 o-alkyl and C(0)-0-Ci- 2 o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-i 0 -alkyl.
  • Ci-io-alkyl and Ci-20-alkyl can be branched or unbranched.
  • Examples of Ci-10-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, fert-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-2o-alkyl examples are Ci-10-alkyl and n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-icosyl (C 2 o).
  • R 100 is at each occurrence Ci- 10 -alkyl or phenyl.
  • Examples of 5 to 14 membered heteroaromatic moieties are the examples given for the 5 to 9 membered heteroaromatic moieties and
  • Preferred compounds of formula (1 ) are of formula
  • the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of
  • X is O, S, Se or N-R 100 ,
  • R 100 is d-10-alkyl or phenyl
  • Y is at each occurrence CH or N .
  • the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of
  • X is O, S or N-R 100 ,
  • R 100 is Ci-10-alkyl or phenyl
  • Y is at each occurrence CH or N .
  • the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of
  • X is O, S or N-R 100 ,
  • R 100 is Ci 10-alkyl or phenyl
  • Y is at each occurrence CH or N .
  • the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of
  • Y is at each occurrence CH or N .
  • Ar 2 is a C6-i4-aromatic moiety, wherein the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-2o-alkyl, O-Ci- 20 -alkyl, C(O)-Ci- 20 -alkyl, C(0)-0-Ci- 2 o-alkyl, phenyl, F, CI and Br,
  • Ci -2 o-alkyl, Ci -2 o-alkyl, 0-Ci -2 o-alkyl, C(0)-Ci -2 o-alkyl and C(0)-0-Ci -2 o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-io-alkyl. More preferably, Ar 2 is a C6-i4-aromatic moiety selected from the group consisting of
  • C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-20-alkyl, O-Ci-20-alkyl, C(O)- Ci-20-alkyl, C(0)-0-Ci-2o-alkyl, phenyl, F, CI and Br,
  • Ci-20-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-2o-alkyl and C(0)-0-Ci-2o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-i 0 -alkyl.
  • p is 1 , 2 or 3. More preferably, p is 1 or 2.
  • n is 0 or 1 . More preferably, n is 0.
  • q is 0, 1 , 2 or 3. More preferably, q is 0 or 1. Most preferably, q is 0.
  • L 1 is selected from the group consisting of
  • R 50 and R 51 are independently from each other H , Ci- 2 o-alkyl, C(0)-Ci- 2 o-alkyl, C(O)- Ci-20-alkenyl, C(0)-phenyl, C(O)-O-Ci- 20 -alkyl, C(0)-0-C 2 -io-alkenyl or C(0)-0-phenyl.
  • L 1 is selected from the group consisting of wherein R 50 and R 51 are independently from each other H or Ci- 2 o-alkyl. Most preferably, L 1 is wherein R 50 and R 51 are H .
  • p 1 , 2, 3, 4, 5 or 6,
  • n 0, 1 or 2
  • q O, 1 , 2, 3, 4, 5 or 6,
  • L 1 is selected from the group consisting of wherein R 50 and R 51 are independently from each other H, Ci- 2 o-alkyl, C(0)-Ci- 2 o-alkyl, C(O)- Ci-20-alkenyl, C(0)-phenyl, C(O)-O-Ci- 20 -alkyl, C(0)-0-C 2 -io-alkenyl or C(0)-0-phenyl,
  • Ar 1 is at each occurrence a 5 to 9 membered heteroaromatic moiety, wherein the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of
  • X is O, S, Se or N-R 100 ,
  • R 100 is Ci- 10 -alkyl or phenyl
  • Y is at each occurrence CH or N, which 5 to 9 membered heteroaromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci- 2 o-alkyl, O-C1-20- alkyl, C(O)-Ci- 20 -alkyl, C(O)-O-Ci- 20 -alkyl, phenyl, F, CI and Br,
  • Ci- 20 -alkyl, Ci- 20 -alkyl, O-Ci- 20 -alkyl, C(0)-Ci- 2 o-alkyl and C(0)-0-Ci- 2 o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-i 0 -alkyl, and
  • Ar 2 is at each occurrence a 5 to 14 membered heteroaromatic moiety or a C6-i4-aromatic moiety, wherein the 5 to 14 membered heteroaromatic moiety and the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci- 2 o-alkyl, C(0)-0-Ci- 2 o-alkyl, phenyl, F, CI and Br,
  • Ci- 20 -alkyl, Ci- 20 -alkyl, O-Ci- 20 -alkyl, C(0)-Ci- 2 o-alkyl and C(0)-0-Ci- 2 o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-i 0 -alkyl.
  • p 1 , 2, 3, 4, 5 or 6
  • n 0, 1 or 2
  • L 1 is selected from the group consisting of wherein R 50 and R 51 are independently from each other H or Ci-20-alkyl,
  • Ar 1 is at each occurrence a 5 to 9 membered heteroaromatic moiety, wherein the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of
  • X is O, S or N-R 100 ,
  • R 100 is Ci-10-alkyl or phenyl
  • Y is at each occurrence CH or N , which 5 to 9 membered heteroaromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci- 2 o-alkyl, O-C1-20- alkyl, C(O)-Ci- 20 -alkyl, C(0)-0-Ci -2 o-alkyl, phenyl, F, CI and Br,
  • Ci-20-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-2o-alkyl and C(0)-0-Ci-2o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and C-i-io-alkyl, and
  • Ar 2 is at each occurrence a 5 to 14 membered heteroaromatic moiety or a C6-i4-aromatic moiety, wherein the 5 to 14 membered heteroaromatic moiety and the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci- 2 o-alkyl, C(0)-0-Ci- 2 o-alkyl, phenyl, F, CI and Br,
  • Ci-20-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-2o-alkyl and C(0)-0-Ci-2o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-i 0 -alkyl.
  • p 1 , 2 or 3
  • n 0 or 1
  • q 0, 1 , or 3
  • L 1 is wherein R 50 and R 51 are H
  • Ar 1 is at each occurrence a 5 to 9 membered heteroaromatic moiety, wherein the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of
  • R 100 is Ci-i 0 -alkyl or phenyl
  • Y is at each occurrence CH or N , which 5 to 9 membered heteroaromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci- 2 o-alkyl, O-Ci- 20 - alkyl, C(0)-Ci- 2 o-alkyl, C(0)-0-Ci -2 o-alkyl, phenyl, F, CI and Br,
  • Ci-20-alkyl, O-Ci-20-alkyl, C(O)-Ci- 20 -alkyl and C(O)-O-Ci- 20 -alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-10-alkyl, and
  • Ar 2 is at each occurrence a C6-i4-aromatic moiety, wherein the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci- 20 -alkyl, O-Ci- 20 -alkyl, C(O)-Ci- 20 -alkyl, C(O)-O-Ci- 20 -alkyl, phenyl, F, CI and Br,
  • Ci- 20 -alkyl, Ci- 20 -alkyl, O-Ci- 20 -alkyl, C(O)-Ci- 20 -alkyl and C(O)-O-Ci- 20 -alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-io-alkyl.
  • p 1 or 2
  • n 0,
  • Ar 1 is at each occurrence a 5 to 9 membered heteroaromatic moiety, wherein the 5 to 9 bered heteroaromatic moiety is selected from the group consisting of
  • Y is at each occurrence CH or N , which 5 to 9 membered heteroaromatic moiety may be substituted with one or more substitu- ents independently from each other selected from the group consisting of Ci- 2 o-alkyl, O-C1-20- alkyl, C(0)-Ci- 2 o-alkyl, C(0)-0-Ci_ 2 o-alkyl, phenyl, F, CI and Br,
  • Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci- 2 o-alkyl and C(0)-0-Ci- 2 o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci_ 10 -alkyl, and
  • Ar 2 is at each occurrence a C6-i4-aromatic moiety selected from the group consisting of
  • C6-i4-aromatic moiety may be substituted with one or more substituents inde- pendently from each other selected from the group consisting of Ci-20-alkyl, O-Ci-20-alkyl, C(O)- Ci-20-alkyl, C(0)-0-Ci-2o-alkyl, phenyl, F, CI and Br,
  • Ci-20-alkyl, Ci- 2 o-alkyl, O-Ci-20-alkyl, C(0)-Ci-2o-alkyl and C(0)-0-Ci_2o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-10-alkyl.
  • substituents independently from each other selected from the group consisting of F, CI, Br and Ci-10-alkyl.
  • the compounds of formula (1 ) are of formula
  • p 1 or 2
  • n 0,
  • Ar 1 is at each occurrence a 5 to 9 membered heteroaromatic moiety, wherein the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of
  • Ci- 2 o-alkyl and C(0)-Ci- 2 o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F and phenyl.
  • Also part of the present invention is a process for preparation of the compounds of formula
  • p 1 , 2, 3, 4, 5 or 6
  • n 0, 1 or 2
  • q is 0, 1 , 2, 3, 4, 5 or 6
  • L 1 is selected from the group consisting of
  • R 50 and R 51 are independently from each other H, Ci-2o-alkyl, C(0)-Ci_2o-alkyl, C(O)- Ci-20-alkenyl, C(0)-phenyl, C(O)-O-Ci- 20 -alkyl, C(0)-0-C 2 -io-alkenyl or C(0)-0-phenyl,
  • Ar 1 is at each occurrence a 5 to 9 membered heteroaromatic moiety, which may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-2o-alkyl, O-Ci- 20 -alkyl, C(O)-Ci- 20 -alkyl, C(O)-O-Ci- 20 -alkyl, phenyl, F, CI and Br, wherein Ci-20-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-2o-alkyl and C(0)-0-Ci-2o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci- 10 -alkyl, and
  • Ar 2 is at each occurrence a 5 to 14 membered heteroaromatic moiety or a C6 i4-aromatic moiety, wherein the 5 to 14 membered heteroaromatic moiety and the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci- 2 o-alkyl, 0-Ci- 2 o-alkyl, C(0)-Ci- 2 o-alkyl, C(0)-0-Ci- 2 o-alkyl, phenyl, F, CI and Br,
  • Ci-20-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-2o-alkyl and C(0)-0-Ci-2o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci- 10 -alkyl, which process comprises the step of treating a compound of formula
  • catalyst I is a palladium catalyst, for example bis(triphenylphosphine)palladium(ll)- chloride.
  • the reaction is performed in a suitable solvent such as tetrahydrofuran.
  • a suitable solvent such as tetrahydrofuran.
  • the reaction is performed at elevated temperatures such as at a temperature in the range of 30 to 100 °C.
  • Also part of the present invention is a process for preparation of the compounds of formula
  • p 1 , 2, 3, 4, 5 or 6
  • n 0, 1 or 2
  • q is O, 1 , 2, 3, 4, 5 or 6 selected from the group consisting of
  • R 50 and R 51 are independently from each other H, Ci- 2 o-alkyl, C(0)-Ci- 2 o-alkyl, C(O)- Ci-2o-alkenyl, C(0)-phenyl, C(O)-O-Ci- 20 -alkyl, C(0)-0-C 2 -io-alkenyl or C(0)-0-phenyl, Ar 1 is at each occurrence a 5 to 9 membered heteroaromatic moiety, which may be substituted with one or more substituents independently from each other selected from the group con- sisting of Ci -2 o-alkyl, O-Ci- 20 -alkyl, C(0)-Ci -2 o-alkyl, C(0)-0-Ci -2 o-alkyl, phenyl, F, CI and Br, wherein Ci- 20 -alkyl, Ci- 20 -alkyl, O-Ci- 20 -alkyl, C(O)-Ci- 20 -alkyl
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-10-alkyl, and
  • Ar 2 is at each occurrence a 5 to 14 membered heteroaromatic moiety or a C6-i4-aromatic moiety, wherein the 5 to 14 membered heteroaromatic moiety and the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-20-alkyl, 0-Ci- 2 o-alkyl, C(0)-Ci- 2 o-alkyl, C(0)-0-Ci-2o-alkyl, phenyl, F, CI and Br,
  • Ci- 2 o-alkyl, Ci- 20 -alkyl, O-Ci- 20 -alkyl, C(O)-Ci- 20 -alkyl and C(O)-O-Ci- 20 -alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci_ 10 -alkyl, which process comprises the step of treating a compound of formula
  • Z 1 is CI, Br, I or OS0 2 CF 3 with a compound of formula
  • Z 2 is CI, Br, I or OS0 2 CF 3 , in the presence of catalyst 11.
  • Catalyst II is preferably a nickel or palladium catalyst, for example Ni(dppp)Cl 2 .
  • the reaction is usually performed in a suitable solvent solvent, for example diethylether.
  • the reaction is usually performed at slightly elevated temperatures such as in the range of 30 to 40 °C.
  • Z 2 is CI, Br, I or OSO2CF3, can be prepared by treating a compound of formula
  • Z 2 is CI, Br, I or OS0 2 CF 3 , with magnesium.
  • the reaction is usually performed in a suitable solvent solvent, for example diethylether.
  • the reaction is usually performed at slightly elevated temperatures such as in the range of 30 to 40 °C.
  • the reaction is usually performed in a suitable solvent such as dimethylformamide.
  • the Z 2 -donor-agent can be N-bromosuccinimide.
  • the compound of formula (3), wherein Z 1 is CI, can be prepared by treating a compound of formula
  • the compound of formula (4) can be prepared by treating a compound of formula
  • p 1 , 2, 3, 4, 5 or 6
  • n 0, 1 or 2
  • q 0, 1 , 2, 3, 4, 5 or 6
  • L 1 is selected from the group consisting of
  • R 50 and R 51 are independently from each other H , Ci-2o-alkyl, C(0)-Ci_2o-alkyl, C(O)- Ci-20-alkenyl, C(0)-phenyl, C(O)-O-Ci- 20 -alkyl, C(0)-0-C 2 -io-alkenyl or C(0)-0-phenyl,
  • Ar 1 is at each occurrence a 5 to 9 membered heteroaromatic moiety, which may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-2o-alkyl, O-Ci- 20 -alkyl, C(O)-Ci- 20 -alkyl, C(O)-O-Ci- 20 -alkyl, phenyl, F, CI and Br, wherein Ci-20-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-2o-alkyl and C(0)-0-Ci-2o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci_ 10 -alkyl, and
  • Ar 2 is at each occurrence a 5 to 14 membered heteroaromatic moiety or a C6-i4-aromatic moiety, wherein the 5 to 14 membered heteroaromatic moiety and the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci- 2 o-alkyl, 0-Ci- 2 o-alkyl, C(0)-Ci- 2 o-alkyl, C(0)-0-Ci- 2 o-alkyl, phenyl, F, CI and Br, wherein Ci-20-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci- 2 o-alkyi and C(0)-0-Ci- 2 o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-io-alkyl.
  • the polymers of the present invention comprise at least 60% by weight of units of formula (10) based on the weight of the polymer.
  • the polymers of the present invention comprise at least 80% by weight of units of formula (10) based on the weight of the polymer.
  • the polymers of the present invention essentially consist of units of formula (10).
  • p 1 , 2, 3, 4, 5 or 6,
  • n 0, 1 or 2
  • q 0, 1 , 2, 3, 4, 5 or 6,
  • L 1 is selected from the group consisting of
  • R 50 and R 51 are independently from each other H, Ci- 2 o-alkyl, C(0)-Ci- 2 o-alkyl, C(O)- Ci-20-alkenyl, C(0)-phenyl, C(O)-O-Ci- 20 -alkyl, C(0)-0-C 2 -io-alkenyl or C(0)-0-phenyl,
  • Ar 1 is at each occurrence a 5 to 9 membered heteroaromatic moiety, wherein the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of
  • R 100 is Ci-10-alkyl or phenyl
  • Y is at each occurrence CH or N, which 5 to 9 membered heteroaromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-20-alkyl, O-C1-20- alkyl, C(0)-Ci-2o-alkyl, C(O)-O-Ci- 20 -alkyl, phenyl, F, CI and Br,
  • Ci-20-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-2o-alkyl and C(0)-0-Ci-2o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-10-alkyl, and
  • Ar 2 is at each occurrence a 5 to 14 membered heteroaromatic moiety or a Ce-M-aromatic moiety, wherein the 5 to 14 membered heteroaromatic moiety and the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci- 20 -alkyl, O-Ci-20-alkyl, C(0)-Ci- 2 o-alkyl, C(0)-0-Ci- 2 o-alkyl, phenyl, F, CI and Br,
  • Ci-20-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci- 2 o-alkyl and C(0)-0-Ci- 2 o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-io-alkyl.
  • p is 1 , 2, 3, 4, 5 or 6
  • n 0, 1 or 2
  • L 1 is selected from the group consisting of wherein R 50 and R 51 are independently from each other H or Ci-20-alkyl,
  • Ar 1 is at each occurrence a 5 to 9 membered heteroaromatic moiety, wherein the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of
  • X is O, S or N-R 100 ,
  • R 100 is Ci-10-alkyl or phenyl
  • Y is at each occurrence CH or N , which 5 to 9 membered heteroaromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci- 2 o-alkyl, O-C1-20- alkyl, C(0)-Ci- 2 o-alkyl , C(0)-0-Ci -2 o-alkyl, phenyl, F, CI and Br,
  • Ci-20-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci- 2 o-alkyl and C(0)-0-Ci- 2 o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl ,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-10-alkyl, and
  • Ar 2 is at each occurrence a 5 to 14 membered heteroaromatic moiety or a C6-i4-aromatic moiety, wherein the 5 to 14 membered heteroaromatic moiety and the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-20-alkyl, 0-Ci- 2 o-alkyl, C(0)-Ci- 2 o-alkyl, C(0)-0-Ci-2o-alkyl, phenyl, F, CI and Br,
  • Ci-20-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci- 2 o-alkyl and C(0)-0-Ci- 2 o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl ,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-10-alkyl.
  • p 1 , 2 or 3
  • n 0 or 1
  • q 0, 1 , or 3
  • L 1 is wherein R 50 and R 51 are H ,
  • Ar 1 is at each occurrence a 5 to 9 membered heteroaromatic moiety, wherein the 5 to 9
  • bered heteroaromatic moiety is selected from the group consisting of
  • X is O, S or N-R 100 ,
  • R 100 is Ci-10-alkyl or phenyl
  • Y is at each occurrence CH or N , which 5 to 9 membered heteroaromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci- 2 o-alkyl, O-Ci- 20 - alkyl, C(O)-Ci- 20 -alkyl, C(O)-O-Ci- 20 -alkyl, phenyl, F, CI and Br,
  • Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci- 2 o-alkyl and C(O)-O-Ci- 20 -alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-10-alkyl, and
  • Ar 2 is at each occurrence a C6-i4-aromatic moiety, wherein the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci- 20 -alkyl, O-Ci- 20 -alkyl, C(O)-Ci- 20 -alkyl, C(O)-O-Ci- 20 -alkyl, phenyl, F, CI and Br,
  • Ci_ 2 o-alkyl, Ci- 2 o-alkyl, 0-Ci_ 2 o-alkyl, C(0)-Ci_ 2 o-alkyl and C(0)-0-Ci_ 2 o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI , Br and phenyl, wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-10-alkyl.
  • the unit of formula (10) is of formula
  • p 1 or 2
  • n 0,
  • Ar 1 is at each occurrence a 5 to 9 membered heteroaromatic moiety, wherein the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of
  • Y is at each occurrence CH or N , which 5 to 9 membered heteroaromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci- 2 o-alkyl, O-Ci- 20 - alkyl, C(O)-Ci- 20 -alkyl, C(0)-0-Ci -2 o-alkyl, phenyl, F, CI and Br,
  • Ci-20-alkyl, O-Ci-20-alkyl, C(O)-Ci- 20 -alkyl and C(0)-0-Ci- 2 o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci_ 10 -alkyl, and
  • Ar 2 is at each occurrence a C6-i4-aromatic moiety selected from the group consisting of wherein the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-20-alkyl, O-Ci-20-alkyl, C(O)- Ci-20-alkyl, C(O)-O-Ci- 20 -alkyl, phenyl, F, CI and Br,
  • Ci- 2 o-alkyl, Ci- 2 o-alkyl, 0-Ci- 2 o-alkyl, C(O)-Ci- 20 -alkyl and C(O)-O-Ci- 20 -alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci_ 10 -alkyl.
  • p 1 or 2
  • n 0,
  • Ar 1 is at each occurrence a 5 to 9 membered heteroaromatic moiety, wherein the 5 to 9 membered heteroaromatic moiety is selected from the group consisting of
  • (A1 b) (B1 b) which 5 to 9 membered heteroaromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci- 20 -alkyl and C(O)- Ci-2o-alkyl, wherein Ci-20-alkyl and C(0)-Ci- 2 o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F and phenyl.
  • Also part of the present invention is a process for the preparation of the polymers comprising unit of formula wherein
  • p 1 , 2, 3, 4, 5 or 6
  • n 0, 1 or 2
  • q 0, 1 , 2, 3, 4, 5 or 6
  • L 1 is selected from the group consisting of
  • R 50 and R 51 are independently from each other H, Ci-20-alkyl, C(0)-Ci-2o-alkyl, Ci-2o-alkenyl, C(0)-phenyl, C(O)-O-Ci- 20 -alkyl, C(0)-0-C 2 -io-alkenyl or C(0)-0-phenyl,
  • Ar 1 is at each occurrence a 5 to 9 membered heteroaromatic moiety, which may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-2o-alkyl, O-Ci- 20 -alkyl, C(O)-Ci- 20 -alkyl, C(O)-O-Ci- 20 -alkyl, phenyl, F, CI and Br, wherein Ci- 2 o-alkyl, Ci- 2 o-alkyl, 0-Ci- 2 o-alkyl, C(0)-Ci- 2 o-alkyl and C(0)-0-Ci- 2 o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-10-alkyl, and
  • Ar 2 is at each occurrence a 5 to 14 membered heteroaromatic moiety or a C6-i4-aromatic moiety, wherein the 5 to 14 membered heteroaromatic moiety and the C6-i4-aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci-2o-alkyl, C(0)-0-Ci-2o-alkyl, phenyl, F, CI and Br, wherein Ci-20-alkyl, Ci-20-alkyl, O-Ci-20-alkyl, C(0)-Ci- 2 o-alkyi and C(0)-0-Ci- 2 o-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-10-alkyl, which process comprises the step of treating a compound of formula
  • p, n, q, L 1 , Ar 1 and Ar 2 are as defined for the polymer comprising a unit of formula (10), and Z 3 is CI, Br or I, with catalyst III.
  • the catalyst III is a nickel catalyst. More preferably, it is an organonickel catalyst such as bis(1 ,5-cyclooctadiene)nickel(0).
  • a chelating ligand such as 2,2'-bipyridine is also present.
  • the reaction is performed in a suitable solvent, for example in dimethyl- formanide (DMF) or tetrahydrofuran or mixtures thereof.
  • the reaction is performed under inert atmosphere.
  • the reaction is performed at elevated temperatures, such as in the range of 40 to 100 °C, preferably 50 to 80 °C.
  • the reaction can be terminated by addition of an endcapper, for example bromobenzene.
  • p, n, q, L 1 , Ar 1 and Ar 2 are as defined for the polymer comprising a unit of formula (10) with a Z 3 -donor-agent.
  • the reaction is usually performed in a suitable solvent such as dimethylformamide or dichloro- methane.
  • a suitable Z 2 -donor.agent is for example N-bromosuccinimide.
  • p 1 , 2, 3, 4, 5 or 6
  • n 0, 1 or 2
  • L 1 is selected from the group consisting of
  • R 50 and R 51 are independently from each other H, Ci-20-alkyl, C(0)-Ci-2o-alkyl, Ci-2o-alkenyl, C(0)-phenyl, C(O)-O-Ci- 20 -alkyl, C(0)-0-C 2 -io-alkenyl or C(0)-0-phenyl,
  • Ar 1 is at each occurrence a 5 to 9 membered heteroaromatic moiety, which may be substituted with one or more substituents independently from each other selected from the group con- sisting of Ci- 20 -alkyl, O-Ci- 20 -alkyl, C(O)-Ci- 20 -alkyl, C(O)-O-Ci- 20 -alkyl, phenyl, F, CI and Br, wherein Ci- 20 -alkyl, Ci- 20 -alkyl, O-Ci- 20 -alkyl, C(O)-Ci- 20 -alkyl and C(O)-O-Ci- 20 -alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl, wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci- 1 0-alkyl, and
  • Ar 2 is at each occurrence a 5 to 14 membered heteroaromatic moiety or a C6-i 4 -aromatic moiety, wherein the 5 to 14 membered heteroaromatic moiety and the C6-i 4 -aromatic moiety may be substituted with one or more substituents independently from each other selected from the group consisting of Ci- 2 o-alkyl, 0-Ci- 2 o-alkyl, C(0)-Ci- 2 o-alkyl, C(0)-0-Ci- 2 o-alkyl, phenyl, F, CI and Br,
  • Ci- 20 -alkyl, Ci- 20 -alkyl, O-Ci- 20 -alkyl, C(O)-Ci- 20 -alkyl and C(O)-O-Ci- 20 -alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and phenyl ,
  • phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, CI, Br and Ci-10-alkyl, and
  • Z 3 is CI, Br or I .
  • Also part of the invention is an electronic device comprising the compounds or the polymers of the present invention.
  • the electronic device can be any electronic device, for example an organic photovoltaic (OPV) cell , an organic field-effect transistor (OFET) or an organic light emitting diode (OLED).
  • OCV organic photovoltaic
  • OFET organic field-effect transistor
  • OLED organic light emitting diode
  • the electronic device is an organic light emitting diode.
  • an organic light emitting diode comprises a substrate, an emission layer comprising an emitting material and a semiconducting material , an anode and a cathode.
  • the organic light emitting diode can comprise additional layers such as enhanced hole injection layers, electron blocking layers and hole blocking layer.
  • An organic light emitting device can have various designs such as a bottom emission design or a top emission design.
  • the substrate of the organic light emitting diode can be glass.
  • the emission layer comprises an emitting material and the compounds or polymers of the present invention.
  • the compounds or polymers of the present invention function as semiconducting material.
  • Examples of emitting materials are fluorescent dyes and phosphorescent dyes.
  • Exam- pies of fluorescent dyes are perylene, rubrene and quinacridone-type dyes as well as Aluminium tris (8-hydroxychinolin) (Alq3) and tris(2-phenylpyridinato-C2,N)iridium(l l l) (l r(ppy)3).
  • the anode is typically indium tin oxide (ITO).
  • the cathode can be LiF/AI.
  • An example of an enhanced hole injection layer is a M0O3 layer.
  • An examples of an electron blocking layer is tris (4-carbazol-9-yl-phenyl)amine (TCTA).
  • An example of a hole blocking layer is 1 ,3,5,-tris(N-phenyl-2-bezimidazolyl)benzene (TPBi).
  • the layers are usually 2 to 100 nm thick, preferably 5 to 50 nm.
  • the layers are usually applied by thermal evaporation.
  • a typical organic light emitting diode is depicted in Figure 1.
  • 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, for example bottom-gate design or top-gate design.
  • the substrate of the organic field effect transistor can be any suitable substrate such as un- doped or highly doped silicon, for example in form of a silicon waver, or glass, or a plastic substrate such as polyethersulfone, polycarbonate, polysulfone, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).
  • the dielectric layer comprises a dielectric material.
  • the dielectric material can be any suitable material such as aluminium oxide, aluminium oxide in combination with a self-assembled monolayer (SAM) of a phosphonic acid such as Ci 4 H 2 9PO(OH)2 [TDPA] or C 7 Fi5Cii H22PO(OH)2 [FODPA]), silicon dioxide, or an organic polymer such as polystyrene (PS), polymethylmethacrylate) (PM MA), poly(4-vinylphenol) (PVP), polyvinyl alcohol) (PVA), benzocyclobutene (BCB) or polyimide (PI), or a combination of these materials
  • SAM self-assembled monolayer
  • a phosphonic acid such as Ci 4 H 2 9PO(OH)2 [TDPA] or C 7 Fi5Cii H22PO(OH)2 [FODPA]
  • silicon dioxide or an organic polymer such as polystyrene (PS), polymethylmethacrylate) (PM MA), poly(4-vinylphenol) (PVP), poly
  • the semiconducting layer of the organic field effect transistor comprises one or more of the compounds 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 source/drain electrodes can be made from any suitable source/drain material, for example silver (Ag), gold (Au) or tantalum (Ta).
  • the source/drain electrodes can have a thickness of 1 to 100 nm, preferably from 5 to 50 nm.
  • the gate electrode can be made from any suitable gate material such as highly doped silicon, aluminium (Al), tungsten (W), indium tin oxide, silver (Ag), gold (Au) or tantalum (Ta), or from a combination of these materials.
  • the gate electrode can have a thickness of 1 to 200 nm, preferably from 5 to 100 nm.
  • the organic field effect transistor can be prepared by methods known in the art.
  • a bottom-gate organic field effect transistor can be prepared as follows:
  • Aluminium can be deposited on highly doped silicon wafers by thermal evaporation, followed by oxidation of the aluminium layer to aluminium oxide and treatment of the aluminium oxide surface with a phosphonic acid in order to form a self-assembled monolayer (SAM-layer) of the phosphonic acid on the aluminium oxide surface.
  • the semiconducting material can be deposited on the SAM-layer by thermal sublimation.
  • the source and drain electrodes can be formed by evaporating gold through a shadow mask.
  • the back side of the highly doped silicon wafers can be coated with silver ink to serve as the gate electrode.
  • a bottom-gate organic field effect transistor can be prepared as follows:
  • Aluminiumoxide can be deposited on highly doped silicon wafers with a thermally grown silicon dioxide layer by atomic layer deposition, followed by treatment of the aluminium oxide surface with a phosphonic acid in order to form a self-assembled monolayer (SAM-layer) of the phosphonic acid on the aluminium oxide surface.
  • the semiconducting material can be deposited on the SAM-layer by thermal sublimation.
  • the source and drain electrodes can be formed by evaporating gold through a shadow mask.
  • the back side of the highly doped silicon wafers can be coated with silver ink to serve as the gate electrode.
  • Also part of the invention is the use of the compounds or polymers of the present invention as semiconducting materials.
  • the compounds and polymers of the present invention are suitable as semiconducting materials for use in electronic devices such as organic photovoltaic (OPV) cells, organic field-effect transistors (OFET) and organic light emitting diodes (OLED).
  • OLED organic photovoltaic
  • OFET organic field-effect transistors
  • OLED organic light emitting diodes
  • the compounds and polymers of the present invention are in particular suitable as semiconducting materials for use in organic light emitting diodes (OLED).
  • the compounds and polymers of the present invention are in particular suitable as semiconducting materials in combination with emitting materials such as fluorescent dyes and phosphorescent dyes, in particular phosphorescent dyes, in the emitting layer of an organic light emitting diode (OLED).
  • the compounds and polymers of the present invention show improved charge carrier transport properties, improved light-emitting properties, and are stable with elapse of time. Examples
  • OLED organic light-emitting diode
  • ITO indium tin oxide
  • the device comprise 10 nm M0O3 for enhanced hole injection, followed by 20 nm tris(4-carba- zol-9-yl-phenyl)amine (TCTA) as an electron blocking layer and a 40nm compound 1 b : tris(2- phenylpyridinato-C2,N)iridium(l ll) (lr(ppy)3), a triplett-emitter, (doping concentration 10wt.%) emission layer.
  • TCTA tris(2- phenylpyridinato-C2,N)iridium(l ll) (lr(ppy)3), a triplett-emitter, (doping concentration 10wt.%) emission layer.
  • the device was capped by a 1 ,3,5-tris(N-phenyl-2-benzimidazolyl)benzene
  • the OLED current density-voltage (J-V) characteristics were recorded with a source measure unit (Keithley 238).
  • the current density-voltage curve for the OLED device comprising lr(ppy)3 as emitting material and compound 1 b as semiconducting material is depicted in Figure 2.
  • the device luminance was calculated from the emission spectrum.
  • the respective spectrometer had been calibrated with a secondary standard calibration halogen lamp (Philips FEL-1000W).
  • Current efficiencies (cd/A) and power efficiencies (Im/W) were calculated from the electrical and optical properties. For this calculation a lambertian light distribution is assumed.
  • the luminance-current density curve for the OLED device comprising lr(ppy)3 as emitting material and compound 1 b as semiconducting material is depicted in Figure 3.
  • the power efficiency-luminance curve for the OLED comprising compound 1 b as lr(ppy)3 as emitting material and compound 1 b as semiconducting material is depicted in Figure 4.
  • the current efficiency-luminance curve for the OLED device comprising lr(ppy)3 as emitting material and compound 1 b as semiconducting material is depicted in Figure 5.
  • Cyclooctadien (COD, 2.25 eq.) and Bis(1 ,5-cyclooctadiene)nickel(0) (2.25 eq.) were dissolved in DM F (0.5 M) under argon atmosphere. 2,2'-Bipyridine (2.25 eq) was added and the color of the solution turned to deep blue. To activate the catalyst, the solution was heated to 50 °C for 30 minutes. Afterwards a solution of compound 9a in THF (0.25 M) was added carefully. The resulting reaction mixture was heated to 60 °C for 30 h. After completion of the reaction 0.01 eq. of endcapper (bromobenzene) were added and the mixture was heated to 60 °C for 2 additional hours.
  • endcapper bromobenzene
  • the reaction mixture was poured into a 1 :2 mixture of hydrochloric acid and methanol.
  • the resulting suspension was transferred into a soxhlet extractor and successively extracted with methanol, aceton and chloroform. Evaporation of the solvent of the chloroform fraction yielded 7% of a red polymer Pa.
  • the average molecular weight was estimated to be

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

La présente invention concerne les composés de formule (1) dans laquelle p vaut 1, 2, 3, 4, 5 ou 6, et 10, Ar1 représente à chaque occurrence une partie hétéroaromatique de 5 à 9 chaînons, qui peut être substituée par un ou plusieurs substituants choisis indépendamment les uns des autres dans l'ensemble consistant en un groupe alkyle en C1-20, O-alkyle en-C1-20, C(O)-alkyle en C1-20, C(O)-O-alkyle en C1-20, phényle, F, Cl et Br, les groupes alkyle en C1-20, alkyle en C1-20, O-alkyle en C1-20, C(O)-alkyle en C1-20 et C(O)-O-alkyle en C1-20 pouvant être substitués par un ou plusieurs substituants choisis indépendamment les uns des autres dans l'ensemble consistant en F, Cl, Br et un groupe phényle, le groupe phényle pouvant être substitué par un ou plusieurs substituants choisis indépendamment les uns des autres dans l'ensemble consistant en F, Cl, Br et un groupe alkyle en C1-10, et des dispositifs électroniques comprenant ces composés.
PCT/IB2014/063478 2013-07-30 2014-07-28 Naphtyridines substituées en tant que molécules acceptrices pour dispositifs électroniques WO2015015397A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017133752A1 (fr) * 2016-02-04 2017-08-10 Merck Patent Gmbh Composés [1,5]-naphthyridine et polymères utilisés comme semi-conducteurs

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009136595A1 (fr) * 2008-05-08 2009-11-12 新日鐵化学株式会社 Composé pour élément électroluminescent à champ électrique, organique, et élément électroluminescent à champ électrique, organique
JP2010215759A (ja) * 2009-03-16 2010-09-30 Konica Minolta Holdings Inc 有機エレクトロルミネッセンス素子、表示装置、照明装置及び有機エレクトロルミネッセンス素子材料
WO2012111811A1 (fr) * 2011-02-18 2012-08-23 コニカミノルタホールディングス株式会社 Élément de conversion photoélectrique organique et photopile

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009136595A1 (fr) * 2008-05-08 2009-11-12 新日鐵化学株式会社 Composé pour élément électroluminescent à champ électrique, organique, et élément électroluminescent à champ électrique, organique
JP2010215759A (ja) * 2009-03-16 2010-09-30 Konica Minolta Holdings Inc 有機エレクトロルミネッセンス素子、表示装置、照明装置及び有機エレクトロルミネッセンス素子材料
WO2012111811A1 (fr) * 2011-02-18 2012-08-23 コニカミノルタホールディングス株式会社 Élément de conversion photoélectrique organique et photopile

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017133752A1 (fr) * 2016-02-04 2017-08-10 Merck Patent Gmbh Composés [1,5]-naphthyridine et polymères utilisés comme semi-conducteurs
CN108602826A (zh) * 2016-02-04 2018-09-28 默克专利有限公司 作为半导体的[1,5]二氮杂萘化合物和聚合物
US11603431B2 (en) 2016-02-04 2023-03-14 Raynergy Tek Incorporation Organic semiconductors

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