EP2707455A1 - Halogenated perylene-based semiconducting materials - Google Patents

Halogenated perylene-based semiconducting materials

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Publication number
EP2707455A1
EP2707455A1 EP12717702.0A EP12717702A EP2707455A1 EP 2707455 A1 EP2707455 A1 EP 2707455A1 EP 12717702 A EP12717702 A EP 12717702A EP 2707455 A1 EP2707455 A1 EP 2707455A1
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EP
European Patent Office
Prior art keywords
substituents
optionally substituted
alkyl
cor
independently
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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EP12717702.0A
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German (de)
French (fr)
Inventor
Helmut Reichelt
Thomas Gessner
Chen Li
Klaus MÜLLEN
Glauco BATTAGLIARIN
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
Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
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BASF SE
Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
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Priority to EP12717702.0A priority Critical patent/EP2707455A1/en
Publication of EP2707455A1 publication Critical patent/EP2707455A1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/08—Naphthalimide dyes; Phthalimide dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/06—Luminescent materials, e.g. electroluminescent or chemiluminescent containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom

Definitions

  • Organic semiconducting materials can be used in electronic devices such as organic photo- voltaic (OPV) cells, organic field-effect transistors (OFETs) and organic light emitting diodes (OLEDs).
  • OCV organic photo- voltaic
  • OFETs organic field-effect transistors
  • OLEDs organic light emitting diodes
  • the organic semiconducting material-based devices show high charge carrier mobility and high stability, in particular towards oxi- dation, under ambient conditions.
  • the organic semiconducting materials are compatible with liquid processing techniques as liquid processing techniques are convenient from the point of proc- essability, and thus allow the production of low cost organic semiconducting material-based electronic devices.
  • liquid processing techniques are also compatible with plastic substrates, and thus allow the production of light weight and flexible organic semiconducting material-based electronic devices.
  • Perylene bisimide-based organic semiconducting materials suitable for use in electronic devices are known in the art.
  • Ar 1 is a first aromatic core and is a divalent, trivalent or tetravalent radical of a long list of formulae, including
  • EC is a first end capping group and is a monovalent radical of a long list of formulae, n is an integer of 2 to 4
  • Z is NH or CH 2
  • OFET organic thin film transistor
  • the organic semiconductor film is formed of pentacene.
  • the organic acceptor film is formed of at least one electron withdrawing material selected from a long list of compounds, including N,N'-bis(di-feri-butyphenyl)-3,4,9,10-perylenedicarboximide.
  • US 7,326,956 B2 describes a thin film transitor comprising a layer of organic semiconductor material comprising tetracarboxylic diimide perylene-based compound having attached to each of the imide nitrogen atoms a carbocyclic or heterocyclic aromatic ring system substituted with one or more fluorine containing groups.
  • the fluorine-containing N,N'-diaryl perylene-based tetracarboxylic diimide compound is represented by the following structure:
  • a 1 and A 2 are independently carbocyclic and/or heterocyclic aromatic ring systems comprising at least one aromatic ring in which one or more hydrogen atoms are substituted with at least one fluorine-containing group.
  • the perylene nucleus can be optionally substituted with up to eight independently selected X groups, wherein n is an integer from 0 to 8.
  • the X substituent groups on the perylene can include a long list of substituents, including halogens such as fluorine or chlorine.
  • each R 1 to R 8 can be independently selected from H, an electron-withdrawing substituent and a moiety comprising such substituent.
  • Electron-withdrawing substitutents include a long list of substituents, including cyano.
  • R 9 and R 10 are independently selected from H, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, polycyclic aryl and/or substi- tuted polycyclic aryl moieties.
  • WO 2005/124453 describes perylenetetracarboxylic diimide charge-transfer materials, for example a perylenetetracarboxylic diimide charge-transfer material having formula
  • Y in each instance can be independently selected from H, CN, acceptors, donors and a polymerizable group; and X in each instance can be independently selected from a large group of listed compounds.
  • WO 2008/063609 describes a compound having the following formula
  • A, B, I, D, E, F, G and H are independently selected from a group of substituents, including, CH and CR a , wherein R a can be selected from a list of substituents, including halogen.
  • A, B, I, D, E, F, G and H can be independently CH, C-Br or C-CN.
  • WO 2009/098252 describes semiconducting compounds having formula
  • R 1 and R 2 at each occurrence independently are selected from a large list of groups, including H, Ci-30-alkyl and C2-3o-alkenyl; and R 3 , R 4 , R 5 and R 6 are independently H or an electron-withdrawing group.
  • R 3 , R 4 , R 5 and R 6 can be independently from each other H, F, CI, Br, I or CN.
  • WO 2009/144205 describes bispolycyclic rylene-based semiconducting compounds, which can be prepared from a compound of formula
  • LG is a leaving group, including CI, Br or I,
  • ⁇ -1 can be
  • A, B, I, D, E, F, G and H are independently selected from a group of substituents, in eluding, CH and CR a , wherein R a can be selected from a list of substituents, including halogen.
  • the object is solved by the compound of claim 1 , the process of claim 5, and the electronic de- vice of claim 6.
  • the perylene-based semiconducting compound of the present invention is of formula 1
  • R 1 and R 2 are independently from each other selected from the group consisting of H, Ci-30-alkyl optionally substituted with 1 to 30 substituents R a , C2-3o-alkenyl optionally substituted with
  • -O-COR 3 -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R', -SO 2 -Ci- 30 -alkyl optionally substituted with 1 to 30 substituents R', -NH 2 , -NHR 3 , -NR 3 R 4 , -[NR 3 R 4 R 5 ] + , -NH-COR 3 , -COOH, -COOR 3 , -CONH 2 , -CONHR 3 , -CONR 3 R 4 , -CO-H, -COR 3 , Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C 2- 3o-alkenyl optionally substituted with 1 to 30 substituents R', C 2- 3o-alkynyl optionally substituted with 1 to 30 substituents R',
  • R 3 , R 4 and R 5 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C 2- 3o-alkenyl optionally substituted with 1 to 30 substituents R', C 2- 3o-alkynyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to
  • R 6 , R 7 and R 8 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, C5-io-cycloalkenyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl,
  • X is -CI, -Br or -I.
  • 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, 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.
  • C3-8-alkyl examples include n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, fert-butyl, n-pentyl, neopentyl, isopentyl, n-(1 -ethyl)propyl, n-hexyl, n-heptyl, n-octyl and n-(2-ethyl)hexyl.
  • Ci-30-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 20 ), n-docosyl (C 22 ), n-tetracosyl (C 2 4), n-hexacosyl (C 2 6), n-octacosyl (C 2 s) and n-triacontyl (C30).
  • C3- 2 5-alkyl branched at the C attached to the N of formula I are isopropyl, sec-butyl, n-(1 -methyl)propyl, n-(1 - ethyl)propyl, n-(1 -methyl)butyl, n-(1 -ethyl)butyl, n-(1 -propyl)butyl, n-(1 -methyl)pentyl, n-(1 - ethyl)pentyl, n-(1 -propyl)pentyl, n-(1 -butyl)pentyl, n-(1 -butyl)hexyl, n-(1 -pentyl)hexyl, n-(1 -pentyl)hexyl, n-(1 - hexyl)heptyl, n-(1 -heptyl)oc
  • C2-3o-alkenyl can be branched or unbranched.
  • Examples of C2-3o-alkenyl are vinyl, propenyl, cis- 2-butenyl, frans-2-butenyl, 3-butenyl, c/s-2-pentenyl, frans-2-pentenyl, c/s-3-pentenyl, trans- 3-pentenyl, 4-pentenyl, 2-methyl-3-butenyl, hexenyl, heptenyl, octenyl, nonenyl and docenyl, linoleyl (ds), linolenyl (Cis), oleyl (Cis), arachidonyl (C20), and erucyl (C22).
  • C2-3o-alkynyl can be branched or unbranched.
  • Examples of C2-3o-alkynyl are ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl and decynyl, undecynyl, do- decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptade- cynyl, octadecynyl, nonadecynyl 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
  • Examples of 3-14 membered cycloheteroalkyi are monocyclic 3-8 membered cycloheteroalkyi and polycyclic, for example bicyclic 7-12 membered cycloheteroalkyi.
  • Examples of monocyclic 3-8 membered cycloheteroalkyi are monocyclic 5 membered cycloheteroalkyi containing one heteroatom such as pyrrolidinyl, 1 -pyrrolinyl, 2-pyrrolinyl, 3-pyrrolinyl, tetrahydrofuryl, 2,3-dihydrofuryl, tetrahydrothiophenyl and 2,3-dihydrothiophenyl, monocyclic
  • cycloheteroalkyi containing one heteroatom such as piperidyl, piperidino, tetrahy- dropyranyl, pyranyl, thianyl and thiopyranyl, monocyclic 6 membered cycloheteroalkyi containing two heteroatoms such as piperazinyl, morpholinyl and morpholino and thiazinyl, monocyclic 7 membered cycloheteroalkyi containing one hereoatom such as azepanyl, azepinyl, oxepanyl, thiepanyl, thiapanyl, thiepinyl, and monocyclic 7 membered cycloheteroalkyi containing two hereoatom such as 1 ,2-diazepinyl and 1 ,3-thiazepinyl.
  • 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.
  • 5-14 membered heteroaryl can be monocyclic 5-8 membered heteroaryl, or polycyclic 7-14 membered heteroaryl, for example bicyclic 7-12 membered or tricyclic 9-14 membered heteroaryl.
  • monocyclic 5-8 membered heteroaryl examples include monocyclic 5 membered heteroaryl con- taining one heteroatom such as pyrrolyl, furyl and thiophenyl, monocyclic 5 membered heteroaryl containing two heteroatoms such as imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, monocyclic 5 membered heteroaryl containing three heteroatoms such as
  • 1 ,2,3-triazolyl, 1 ,2,4-triazolyl and oxadiazolyl monocyclic 5 membered heteroaryl containing four heteroatoms such as tetrazolyl, monocyclic 6 membered heteroaryl containing one heteroa- torn such as pyridyl, monocyclic 6 membered heteroaryl containing two heteroatoms such as pyrazinyl, pyrimidinyl and pyridazinyl, monocyclic 6 membered heteroaryl containing three heteroatoms such as 1 ,2,3-triazinyl, 1 ,2,4-triazinyl and 1 ,3,5-triazinyl, monocyclic 7 membered heteroaryl containing one heteroatom such as azepinyl, and monocyclic 7 membered heteroaryl containing two heteroatoms such as 1 ,2-diazepinyl.
  • monocyclic 5 membered heteroaryl containing four heteroatoms such as
  • bicyclic 7-12 membered heteroaryl examples include bicyclic 9 membered heteroaryl containing one heteroatom such as indolyl, isoindolyl, indolizinyl, indolinyl, benzofuryl, isobenzofuryl, ben- zothiophenyl and isobenzothiophenyl, bicyclic 9 membered heteroaryl containing two heteroatoms such as indazolyl, benzimidazolyl, benzimidazolinyl, benzoxazolyl, benzisooxazolyl, benzthiazolyl, benzisothiazolyl, furopyridyl and thienopyridyl, bicyclic 9 membered heteroaryl containing three heteroatoms such as benzotriazolyl, benzoxadiazolyl, oxazolopyridyl, isooxa- zolopyridyl, thiazolopyridyl, iso
  • tricyclic 9-14 membered heteroaryls examples include dibenzofuryl, acridinyl, phenoxazinyl, 7H- cyclopenta[1 ,2-b:3,4-b']dithiophenyl and 4H-cyclopenta[2,1 -b:3,4-b']dithiophenyl.
  • halogen examples are -F, -CI, -Br and -I.
  • Ci-30-alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, fert-butoxy, n-pentoxy, neopentoxy, isopentoxy, hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dodecoxy, n-tridecoxy, n-tetradecoxy, n-pentadecoxy, n-hexadecoxy, n-heptadecoxy, n-octadecoxy and n-nonadecoxy.
  • Examples of C2-5-alkylene are ethylene, propylene, butylene and pentylene.
  • C2-5-alkylene are ethylene, prop
  • R 1 and R 2 are independently from each other selected from the group consisting of H, Ci-30-alkyl optionally substituted with 1 to 30 substituents R a , C2-3o-alkenyl optionally substituted with 1 to 30 substituents R a , C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R b , and C6-i4-aryl optionally substituted with 1 to 8 substituents R c , wherein
  • R 3 , R 4 and R 5 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C2-3o-alkenyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents R iH ,
  • R 6 , R 7 and R 8 at each occurrence are independently from each other selected from the group consisting of Ci -3 o-alkyl, C 2-3 o-alkenyl, C 3- io-cycloalkyl, and C6-i4-aryl, and
  • X is -CI, -Br or I.
  • R 1 and R 2 are independently from each other Ci -3 o-alkyl optionally substituted with 1 to 30 substituents R a , wherein
  • R 3 , R 4 and R 5 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C2-3o-alkenyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents R iH ,
  • R 6 , R 7 and R 8 at each occurrence are independently from each other selected from the group consisting of Ci -3 o-alkyl, C 2-3 o-alkenyl, C 3- io-cycloalkyl, and C6-i4-aryl, and
  • X is -CI, -Br or -I. Most preferably,
  • R 1 and R 2 are independently from each other C 3-2 5-alkyl branched at the C attached to the N of formula 1 and
  • X is -CI, -Br or -I. Particular preferred are the compounds of formulae
  • R 1 and R 2 are as defined above, which process comprises the steps of
  • R 1 and R 2 are as defined above, and L is a linking group
  • L is preferably C2-5-alkylene, which can be optionally substituted with 1 to 6 Ci-10-alkyl groups. More preferably L is ethylene or propylene and is substituted with 2 to 4 methyl groups.
  • the transition metal-containing catalyst can be an iridium-containing catalyst such as
  • the first step can be performed in the presence of a base such as di-feri-butylbipyridine. If the transition metal- containing catalyst is an iridium-containing catalyst, the first step is usually performed in a suitable organic solvent such as tetrahydrofuran or 1 ,4-dioxane. If the transition metal-containing catalyst is an iridium-containing catalyst, the first step is usually performed at elevated temperatures, such as at temperatures from 60 to 1 10 °C. In principal, if the transition metal-containing catalyst is an iridium-containing catalyst, the first step can be performed in analogy to the method described by C. W. Liskey; X. Liao; J. F.
  • the first step is usu- ally performed in a suitable organic solvent such as toluene, pinacolone and mesitylene or mixtures thereof. If the transition metal-containing catalyst is ruthenium-containing catalyst, the first step is usually performed at elevated temperatures, such as at temperatures from 120 to 160 °C.
  • the Cl-source source can be Cu(ll)Cl2.
  • the Br-source source can be Cu(ll)Br2.
  • the l-source source can be Nal in combination with chloroamine T.
  • the second step is usually performed in a suitable solvent such as water, methanol, THF and dioxane, or mixtures thereof.
  • the second step is usually performed at elevated temperatures, such as at temperatures from 40 to 140 °C.
  • the second step is preferably performed at elevated temperatures, such as at temperatures from 80 to 140 °C.
  • the second step is preferably performed at elevated temperatures, such as at temperatures from 40 to 80 °C.
  • the compounds of formulae (4) and (1 ) can be isolated by methods known in the art, such as column chromatography.
  • the compound of formula (2) can be obtained by methods known in the art, for example as described in the subsection titled "Synthesis" of F. Wurthner, Chem. Commun., 2004, 1564-1579.
  • an electronic device comprising the compound of formula (1 ) as semiconducting material.
  • the electronic device is an organic field effect transistor (OFET).
  • 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. The most common design of an organic field-effect transistor is the bottom-gate design. Examples of bottom-gate designs are shown in Figures 1.
  • top-gate design Another design of an organic field-effect transistor is the top-gate design. Examples of top-gate designs are shown in Figure 2.
  • 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 silicon dioxide, or, an organic polymer such as polystyrene (PS), poly(methylmethacrylate) (PMMA), poly(4-vinylphenol) (PVP), polyvinyl alcohol) (PVA), benzocyclobutene (BCB), or polyimide (PI).
  • PS polystyrene
  • PMMA poly(methylmethacrylate)
  • PVP poly(4-vinylphenol)
  • PVA polyvinyl alcohol
  • BCB benzocyclobutene
  • 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 electrodes can be made from any suitable source/drain material, for example 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, gold (Au) and/or tantalum (Ta).
  • the gate elec- trode can have a thickness of 1 to 200 nm, preferably from 5 to 100 nm.
  • the substrate can be any suitable substrate such as glass, or a plastic substrate such as poly- ethersulfone, polycarbonate, polysulfone, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).
  • a combination of the gate electrode and the dielectric layer can also function as substrate.
  • 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:
  • the gate electrode can be formed by depositing the gate material, for example highly doped silicon, on one side of the dielectric layer made of a suitable dielectric material, for example si- licium dioxide.
  • the other side of the dielectric layer can be optionally treated with a suitable reagent, for example with hexamethyldisilazane (HMDS).
  • Source/drain electrodes can be deposited on this side (the side which is optionally treated with a suitable reagent) of the dielectric layer for example by vapour deposition of a suitable source/drain material, for example tantalum (Ta) and/or gold (Au).
  • the source/drain electrodes can then be covered with the semiconducting layer by solution processing, for example drop coating, a solution of the semiconducting material of the present invention in s suitable solvent, for example in chloroform. Also part of the invention is the use of the compound of formula (1 ) as semiconducting material.
  • the advantage of the semiconducting materials of the present invention is the high solubility of these materials in solvents suitable for solution processing.
  • the semiconducting materials of the present invention show acceptable to high charge carrier mobility.
  • the semiconducting materials are stable, in particular towards oxidation, under ambient conditions.
  • A/,A/'-Bis(1 -heptyloctyl) perylene-3,4:9,10-tetracarboxylic acid bisimide (2b) (100 mg, 0.12 mmol) and bispinacolonediboronate (3a) (250 mg, 0.99 mmol) are mixed together and dissolved in 1 ml. anhydrous mesitylene and 1 ml. anhydrous pinacolone. Argon is bubbled through the solution for 30 minutes.
  • RuH2(CO)(PPh3)3 23 mg, 0,03 mmol
  • thermoly grown silicon dioxide (thickness: 200 nm) is used as dielectric layer.
  • the gate electrode is formed by depositing highly doped silicon on one side of the dielectric layer.
  • the other side of the dielectric layer is treated with hexamethyldisilazane (HMDS) by vapour deposition of hexamethyldisilazane.
  • HMDS hexamethyldisilazane
  • the contact angle of the surface of the HMPS-treated side of the dielectric layer is 93.2 ⁇ 1.3°.
  • Source/drain electrodes (Ta (thickness: 10 nm) covered by Au (thick- ness: 40 nm)) are deposited on the HMPS-treated side of the dielectric layer by vapour deposition.
  • the source/drain electrodes are then covered with the semiconducting layer (thickness: ca.
  • the drain current ISD [A] in relation to the gate voltage VSG [V] (top transfer curve) and the drain current ISD 0 5 [ ⁇ ° 5 ] in relation to the gate voltage VSG [V] (bottom transfer curve) for the bottom- gate organic field effect transistor of example 6 comprising compound 1c as semiconducting material at a drain voltage VSD of 100 V is determined in a nitrogen filled glove box (O2 content: 0.1 ppm, H 2 0 content: 0.0 ppm, pressure: 1 120 Pa, temperature: 17 °C) using a Keithley 4200 machine is shown. The results are shown in Figure 4.
  • the drain current ISD in relation to the drain voltage VSD (output curve) for the bottom-gate organic field effect transistor of example 6 comprising compound 1c as semiconducting material at a gate voltage VSG of 100 V (first and top curve), 90 V (second curve), 80 V (third curve), 70 V (fourth curve) and 0 V (fifth and bottom curve) is determined in a nitrogen filled glove box (O2 content: 0.1 ppm, H2O content: 0.0 ppm, pressure: 1 120 Pa, temperature: 17 °C) using a Keithley 4200 machine is shown. The results are shown in Figure 5.
  • drain current ISD [A] in relation to the gate voltage VSG [V] (top transfer curve) and the drain current ISD 0 5 [ ⁇ ° 5 ] in relation to the gate voltage VSG [V] (bottom transfer curve) for the bottom- gate, organic field effect transistor of example 6 comprising compound 1 b as semiconducting material at a drain voltage VSD of 100 V is determined in a nitrogen filled glove box (O2 content: 0.1 ppm, H 2 0 content: 0.0 ppm, pressure: 1 120 Pa, temperature: 17 °C) using a Keithley 4200 machine is shown. The results are shown in Figure 6.
  • the drain current ISD in relation to the drain voltage VSD (output curve) for the bottom-gate organic field effect transistor of example 6 comprising compound 1 b as semiconducting material at a gate voltage VSG of 100 V (first and top curve), 90 V (second curve), 80 V (third curve) and 0 V (fourth and bottom curve) is determined in a nitrogen filled glove box (O2 content: 0.1 ppm, H2O content: 0.0 ppm, pressure: 1 120 Pa, temperature: 17 °C) using a Keithley 4200 machine is shown. The results are shown in Figure 7.
  • the average values and the 90% confidence interval (in parentheses) of the charge carrier mobilities ⁇ 53 ⁇ [cmWs], the ION/IOFF ratios and the switch-on voltages Vso [V] for the bottom-gate organic field effect transistors of example 6 comprising compound 1 b, respectively, 1c, as semi- conducting material are given in table 1.
  • the switch-on voltage Vso [V] is the gate voltage VSG [V] where the drain current ISD [A] starts to increase (out of the off-state).
  • A/,A/'-Bis-octyl-2,5,8,1 1 -tetrakis[4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-y]perylene-3,4:9,10- tetracarboxylic acid bisimide (0.68 mg, 0.61 mmol) and copper(ll) bromide (1 ,62 g, 7.3 mmol) are suspended in a mixture of dioxane (10 mL), methanol (3 ml) and water (3 ml) and heated at 120°C for 12 hours. The reaction mixture is then poured into HCI (1 .0 M) and the solid so obtained filtered.

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Abstract

The present invention provides a compound of formula (1) wherein X is -Cl, -Br or -I. The compound of formula (1) is suitable for use as semiconducting material, in particular in electronic devices.

Description

Halogenated Perylene-based Semiconducting Materials
Description
Organic semiconducting materials can be used in electronic devices such as organic photo- voltaic (OPV) cells, organic field-effect transistors (OFETs) and organic light emitting diodes (OLEDs).
For efficient and long lasting performance, it is desirable that the organic semiconducting material-based devices show high charge carrier mobility and high stability, in particular towards oxi- dation, under ambient conditions.
Furthermore, it is desirable that the organic semiconducting materials are compatible with liquid processing techniques as liquid processing techniques are convenient from the point of proc- essability, and thus allow the production of low cost organic semiconducting material-based electronic devices. In addition, liquid processing techniques are also compatible with plastic substrates, and thus allow the production of light weight and flexible organic semiconducting material-based electronic devices.
Perylene bisimide-based organic semiconducting materials suitable for use in electronic devices are known in the art.
F. Wurthner Chem. Commun. 2004, 1564-1579 describes perylene bisimide derivatives, for example
R. Schmidt, J. H. Oh, Y.-S. Sun, M. Deppisch, A.-M. Krause, K. Radacki, H. Braunschweig, M. Konemann, P. Erk, Z. Bao and F. Wurthner J. Am. Chem. Soc. 2009, 131, 6215-6228 describes halogenated perylene bisimide derivatives, for example
M. Gsanger, J. H. Oh, M. Konemann, H. W. Hoffken, A.-M. Krause, Z. Bao, F. Wurthner Angew. Chem. 2010, 122, 752-755 describes the following halogenated perylene bisimide
S. Nakazono, Y. Imazaki, H. Yoo, J. Yang, T. Sasamori, N. Tokitoh, T. Cedric, H. Kageyama, D. Kim, H. Shinokubo and A. Osuka Chem. Eur. J. 2009, 15, 7530-7533 describes the preparation of 2,5,8,1 1 tetraalkylated perylene tetracarboxylic acid bisimides from perylene tetracarboxylic acid bisimides
S. Nakanzono, S. Easwaramoorthi, D. Kim, H. Shinokubo, A. Osuka Org. Lett. 2009, 11, 5426 to 5429 describes the preparation of 2,5,8,1 1 tetraarylated perylene tetracarboxylic acid bisimides from perylene tetracarboxylic acid bisimides
US 7,282,275 B2 describes a composition that includes
a first compound of formula [EC-]n-Ar1 (I), wherein
Ar1 is a first aromatic core and is a divalent, trivalent or tetravalent radical of a long list of formulae, including
that is unsubstituted or substituted with a long list of substituents, including fluoro,
EC is a first end capping group and is a monovalent radical of a long list of formulae, n is an integer of 2 to 4
Z is NH or CH2, and a second compound having an aromatic radical that comprises the first aromatic core of the first compound, a second end capping group that comprises the first end capping group of the first compound, a divalent radical that comprises a divalent radical of the first end capping group, or a combination thereof, wherein the composition is amorphous and solution proccessible.
US 7,355,198 B2 describes an organic thin film transistor (OFET), which interposes an organic acceptor film between source and drain electrodes and an organic semiconductor film. The organic semiconductor film is formed of pentacene. In particular, the organic acceptor film is formed of at least one electron withdrawing material selected from a long list of compounds, including N,N'-bis(di-feri-butyphenyl)-3,4,9,10-perylenedicarboximide.
US 7,326,956 B2 describes a thin film transitor comprising a layer of organic semiconductor material comprising tetracarboxylic diimide perylene-based compound having attached to each of the imide nitrogen atoms a carbocyclic or heterocyclic aromatic ring system substituted with one or more fluorine containing groups. In one embodiment the fluorine-containing N,N'-diaryl perylene-based tetracarboxylic diimide compound is represented by the following structure:
wherein A1 and A2 are independently carbocyclic and/or heterocyclic aromatic ring systems comprising at least one aromatic ring in which one or more hydrogen atoms are substituted with at least one fluorine-containing group. The perylene nucleus can be optionally substituted with up to eight independently selected X groups, wherein n is an integer from 0 to 8. The X substituent groups on the perylene can include a long list of substituents, including halogens such as fluorine or chlorine.
US 7,671 ,202 B2 describes n-type semiconductor compounds of formula
wherein each R1 to R8 can be independently selected from H, an electron-withdrawing substituent and a moiety comprising such substituent. Electron-withdrawing substitutents include a long list of substituents, including cyano. R9 and R10 are independently selected from H, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, aryl, substituted aryl, polycyclic aryl and/or substi- tuted polycyclic aryl moieties. WO 2005/124453 describes perylenetetracarboxylic diimide charge-transfer materials, for example a perylenetetracarboxylic diimide charge-transfer material having formula
wherein Y in each instance can be independently selected from H, CN, acceptors, donors and a polymerizable group; and X in each instance can be independently selected from a large group of listed compounds.
WO 2008/063609 describes a compound having the following formula
R1
wherein Q can be
wherein A, B, I, D, E, F, G and H are independently selected from a group of substituents, including, CH and CRa, wherein Ra can be selected from a list of substituents, including halogen. For example, A, B, I, D, E, F, G and H can be independently CH, C-Br or C-CN. WO 2009/098252 describes semiconducting compounds having formula
wherein R1 and R2 at each occurrence independently are selected from a large list of groups, including H, Ci-30-alkyl and C2-3o-alkenyl; and R3, R4, R5 and R6 are independently H or an electron-withdrawing group. In certain embodiments, R3, R4, R5 and R6 can be independently from each other H, F, CI, Br, I or CN.
WO 2009/144205 describes bispolycyclic rylene-based semiconducting compounds, which can be prepared from a compound of formula
wherein LG is a leaving group, including CI, Br or I,
π-1 can be
wherein A, B, I, D, E, F, G and H are independently selected from a group of substituents, in eluding, CH and CRa, wherein Ra can be selected from a list of substituents, including halogen.
So far, it has not been possible to prepare 2,5,8,1 l -tetrahalogenoperylene-bis(dicarboximides).
It was the object of the present invention to provide new perylene-based semiconducting materials.
The object is solved by the compound of claim 1 , the process of claim 5, and the electronic de- vice of claim 6.
The perylene-based semiconducting compound of the present invention is of formula 1
wherein
R1 and R2 are independently from each other selected from the group consisting of H, Ci-30-alkyl optionally substituted with 1 to 30 substituents Ra, C2-3o-alkenyl optionally substituted with
1 to 30 substituents Ra, C2-3o-alkynyl optionally substituted with 1 to 30 substituents Ra, C3-io-cycloalkyl optionally substituted with 1 to 10 substituents Rb, Cs-io-cycloalkenyl optionally substituted with 1 to 10 substituents Rb, 3-14 membered cycloheteroalkyl optionally substituted with 1 to 8 substituents Rb, C6-i4-aryl optionally substituted with 1 to 8 substitu- ents Rc and 5-14 membered heteroaryl optionally substituted with 1 to 8 substituents Rc, wherein
Ra at each occurrence are independently from each other selected from the group consist- ing of halogen, -CN , -NO2, -IM3, -OH , Ci-30-alkoxy optionally substituted with 1 to 6 substituents R, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR3, -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R', -S02-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R', -N H2, -N H R3, -N R3R4, -[N R3R4R5]+, -N H-COR3, -COOH , -COOR3, -CON H2, -CON H R3, -CON R3R4, -CO-H , -COR3, C3-io-cyclo- alkyl optionally substituted with 1 to 10 substituents R", Cs-io-cycloalkenyl optionally substi- tuted with 1 to 10 substituents R", 3-14 membered cycloheteroalkyi optionally substituted with 1 to 10 substituents R", C6-i4-aryl optionally substituted with 1 to 8 substituents R'" and 5-14 membered heteroaryl optionally substituted with 1 to 8 substituents R'"; Rb at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -NO2, -OH, Ci-30-alkoxy optionally substituted with 1 to 30 substituents
-0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR3, -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R', -NH2, -NHR3, -NR3R4, -[NR3R4R5]+, -NH-COR3, -COOH, -COOR3, -CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, Ci-3o-alkyl optionally substituted with 1 to 30 substituents R', C2-3o-alkenyl optionally substituted with 1 to 30 substituents R', C2-3o-alkynyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", Cs-io-cycloalkenyl optionally substituted with 1 to 10 substituents R", 3-14 membered cycloheteroalkyi optionally substituted with 1 to 10 substituents R",C6-i4-aryl optionally substituted with 1 to 8 sub- stituents R'" and 5-14 membered heteroaryl optionally substituted with 1 to 8 substituents
R"';
Rc at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -IM3, -OH, Ci-30-alkoxy optionally substituted with 1 to 30 sub- stituents R', -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10),
-O-COR3, -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R', -SO2-Ci-30-alkyl optionally substituted with 1 to 30 substituents R', -NH2, -NHR3, -NR3R4, -[NR3R4R5]+, -NH-COR3, -COOH, -COOR3, -CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C2-3o-alkenyl optionally substituted with 1 to 30 substituents R', C2-3o-alkynyl optionally substituted with 1 to 30 substituents R',
C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", Cs-io-cycloalkenyl optionally substituted with 1 to 10 substituents R", 3-14 membered cycloheteroalkyi optionally substituted with 1 to 10 substituents R", C6-i4-aryl optionally substituted with 1 to 8 substituents R'" and 5-14 membered heteroaryl optionally substituted with 1 to 8 substituents R'"; wherein
R3, R4 and R5 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C2-3o-alkenyl optionally substituted with 1 to 30 substituents R', C2-3o-alkynyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to
10 substituents R", Cs-io-cycloalkenyl optionally substituted with 1 to 10 substituents R", 3-14 membered cycloheteroalkyi optionally substituted with 1 to 10 substituents R", C6-i4-aryl optionally substituted with 1 to 8 substituents R'" and 5-14 membered heteroaryl optionally substituted with 1 to 8 substituents R'",
R' at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -N3, -OH, Ci-30-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR3, -S-Ci-30-alkyl, -SO2-Ci-30-alkyl, -NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR6, -COOH, -COOR6, -CONH2, -CONHR6, -CONR6R7, -CO-H, -COR6, C3-io-cycloalkyl, C5-io-cycloalkenyl, 3-14 membered cyclo- heteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl,
R" at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -OH, Ci-30-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR6, -S-Ci-so-alkyl, -NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR6, -COOH, -COOR6, -CONH2, -CONHR6, -CONR6R7, - CO-H, -COR6, Ci-3o-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, C5-10- cycloalkenyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl,
RiN at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -N3, -OH, Ci-30-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR6, -S-Ci-30-alkyl, -SO2-Ci-30-alkyl, -NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR6, -COOH, -COOR6, -CONH2, -CONHR6, -CONR6R7, -CO-H, -COR6, Ci-3o-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, C5-io-cycloalkenyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl, wherein
R6, R7 and R8 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, C5-io-cycloalkenyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl,
and X is -CI, -Br or -I.
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, 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. Examples of C3-8-alkyl are n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, fert-butyl, n-pentyl, neopentyl, isopentyl, n-(1 -ethyl)propyl, n-hexyl, n-heptyl, n-octyl and n-(2-ethyl)hexyl. Examples of Ci-30-alkyl 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 (C20), n-docosyl (C22), n-tetracosyl (C24), n-hexacosyl (C26), n-octacosyl (C2s) and n-triacontyl (C30). Examples of C3-25-alkyl branched at the C attached to the N of formula I are isopropyl, sec-butyl, n-(1 -methyl)propyl, n-(1 - ethyl)propyl, n-(1 -methyl)butyl, n-(1 -ethyl)butyl, n-(1 -propyl)butyl, n-(1 -methyl)pentyl, n-(1 - ethyl)pentyl, n-(1 -propyl)pentyl, n-(1 -butyl)pentyl, n-(1 -butyl)hexyl, n-(1 -pentyl)hexyl, n-(1 - hexyl)heptyl, n-(1 -heptyl)octyl, n-(1 -octyl)nonyl, n-(1 -nonyl)decyl, n-(1 -decyl)undecyl, undecyl)dodecyl and n-(1 -dodecyl)tridecyl.
C2-3o-alkenyl can be branched or unbranched. Examples of C2-3o-alkenyl are vinyl, propenyl, cis- 2-butenyl, frans-2-butenyl, 3-butenyl, c/s-2-pentenyl, frans-2-pentenyl, c/s-3-pentenyl, trans- 3-pentenyl, 4-pentenyl, 2-methyl-3-butenyl, hexenyl, heptenyl, octenyl, nonenyl and docenyl, linoleyl (ds), linolenyl (Cis), oleyl (Cis), arachidonyl (C20), and erucyl (C22).
C2-3o-alkynyl can be branched or unbranched. Examples of C2-3o-alkynyl are ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl and decynyl, undecynyl, do- decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptade- cynyl, octadecynyl, nonadecynyl 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 3-14 membered cycloheteroalkyi are monocyclic 3-8 membered cycloheteroalkyi and polycyclic, for example bicyclic 7-12 membered cycloheteroalkyi. Examples of monocyclic 3-8 membered cycloheteroalkyi are monocyclic 5 membered cycloheteroalkyi containing one heteroatom such as pyrrolidinyl, 1 -pyrrolinyl, 2-pyrrolinyl, 3-pyrrolinyl, tetrahydrofuryl, 2,3-dihydrofuryl, tetrahydrothiophenyl and 2,3-dihydrothiophenyl, monocyclic
5 membered cycloheteroalkyi containing two heteroatoms such as imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, oxazolidinyl, oxazolinyl, isoxazolidinyl, isoxazolinyl, thiazolidinyl, thia- zolinyl, isothiazolidinyl and isothiazolinyl, monocyclic 5 membered cycloheteroalkyi containing three heteroatoms such as 1 ,2,3-triazolyl, 1 ,2,4-triazolyl and 1 ,4,2-dithiazolyl, monocyclic
6 membered cycloheteroalkyi containing one heteroatom such as piperidyl, piperidino, tetrahy- dropyranyl, pyranyl, thianyl and thiopyranyl, monocyclic 6 membered cycloheteroalkyi containing two heteroatoms such as piperazinyl, morpholinyl and morpholino and thiazinyl, monocyclic 7 membered cycloheteroalkyi containing one hereoatom such as azepanyl, azepinyl, oxepanyl, thiepanyl, thiapanyl, thiepinyl, and monocyclic 7 membered cycloheteroalkyi containing two hereoatom such as 1 ,2-diazepinyl and 1 ,3-thiazepinyl.
An example of a bicyclic 7-12 membered cycloheteroalkyi is decahydronaphthyl. 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. 5-14 membered heteroaryl can be monocyclic 5-8 membered heteroaryl, or polycyclic 7-14 membered heteroaryl, for example bicyclic 7-12 membered or tricyclic 9-14 membered heteroaryl.
Examples of monocyclic 5-8 membered heteroaryl are monocyclic 5 membered heteroaryl con- taining one heteroatom such as pyrrolyl, furyl and thiophenyl, monocyclic 5 membered heteroaryl containing two heteroatoms such as imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, monocyclic 5 membered heteroaryl containing three heteroatoms such as
1 ,2,3-triazolyl, 1 ,2,4-triazolyl and oxadiazolyl, monocyclic 5 membered heteroaryl containing four heteroatoms such as tetrazolyl, monocyclic 6 membered heteroaryl containing one heteroa- torn such as pyridyl, monocyclic 6 membered heteroaryl containing two heteroatoms such as pyrazinyl, pyrimidinyl and pyridazinyl, monocyclic 6 membered heteroaryl containing three heteroatoms such as 1 ,2,3-triazinyl, 1 ,2,4-triazinyl and 1 ,3,5-triazinyl, monocyclic 7 membered heteroaryl containing one heteroatom such as azepinyl, and monocyclic 7 membered heteroaryl containing two heteroatoms such as 1 ,2-diazepinyl.
Examples of bicyclic 7-12 membered heteroaryl are bicyclic 9 membered heteroaryl containing one heteroatom such as indolyl, isoindolyl, indolizinyl, indolinyl, benzofuryl, isobenzofuryl, ben- zothiophenyl and isobenzothiophenyl, bicyclic 9 membered heteroaryl containing two heteroatoms such as indazolyl, benzimidazolyl, benzimidazolinyl, benzoxazolyl, benzisooxazolyl, benzthiazolyl, benzisothiazolyl, furopyridyl and thienopyridyl, bicyclic 9 membered heteroaryl containing three heteroatoms such as benzotriazolyl, benzoxadiazolyl, oxazolopyridyl, isooxa- zolopyridyl, thiazolopyridyl, isothiazolopyridyl and imidazopyridyl, bicyclic 9 membered heteroaryl containing four heteroatoms such as purinyl, bicyclic 10 membered heteroaryl containing one heteroatom such as quinolyl, isoquinolyl, chromenyl and chromanyl, bicyclic 10 membered heteroaryl containing two heteroatoms such as quinoxalinyl, quinazolinyl, cinnolinyl, phthalaz- inyl, 1 ,5-naphthyridinyl and 1 ,8-naphthyridinyl, bicyclic 10 membered heteroaryl containing three heteroatoms such as pyridopyrazinyl, pyridopyrimidinyl and pyridopyridazinyl, and bicyclic 10 membered heteroaryl containing four heteroatoms such as pteridinyl. Examples of tricyclic 9-14 membered heteroaryls are dibenzofuryl, acridinyl, phenoxazinyl, 7H- cyclopenta[1 ,2-b:3,4-b']dithiophenyl and 4H-cyclopenta[2,1 -b:3,4-b']dithiophenyl.
Examples of halogen are -F, -CI, -Br and -I. Examples of Ci-30-alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, fert-butoxy, n-pentoxy, neopentoxy, isopentoxy, hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dodecoxy, n-tridecoxy, n-tetradecoxy, n-pentadecoxy, n-hexadecoxy, n-heptadecoxy, n-octadecoxy and n-nonadecoxy. Examples of C2-5-alkylene are ethylene, propylene, butylene and pentylene. Preferably,
R1 and R2 are independently from each other selected from the group consisting of H, Ci-30-alkyl optionally substituted with 1 to 30 substituents Ra, C2-3o-alkenyl optionally substituted with 1 to 30 substituents Ra, C3-io-cycloalkyl optionally substituted with 1 to 10 substituents Rb, and C6-i4-aryl optionally substituted with 1 to 8 substituents Rc, wherein
Ra at each occurrence are independently from each other selected from the group consisting of halogen, -CN , -NO2, -IM3, -OH , Ci-30-alkoxy optionally substituted with 1 to 6 substitu- ents R', -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10),
-O-COR3, -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R', -SO2-Ci-30-alkyl optionally substituted with 1 to 30 substituents R', -N H2, -N H R3, -N R3R4, -[N R3R4R5]+, -N H-COR3, -COOH , -COOR3, -CON H2, -CON H R3, -CON R3R4, -CO-H , -COR3, C3-io-cyclo- alkyl optionally substituted with 1 to 10 substituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents RiH;
Rb at each occurrence are independently from each other selected from the group consisting of halogen, -CN , -N02, -OH , Ci-30-alkoxy optionally substituted with 1 to 30 substituents R, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR3, -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R', -N H2, -N H R3, -N R3R4,
-[N R3R4R5]+, -N H-COR3, -COOH , -COOR3, -CON H2, -CON H R3, -CON R3R4, -CO-H , -COR3, Ci-3o-alkyl optionally substituted with 1 to 30 substituents R', C2-3o-alkenyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents R'";
Rc at each occurrence are independently from each other selected from the group consisting of halogen, -CN , -N02, -N3, -OH , Ci-30-alkoxy optionally substituted with 1 to 30 substituents R, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR3, -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R', -SO2-Ci-30-alkyl optionally substituted with 1 to 30 substituents R', -N H2, -N H R3, -N R3R4, -[N R3R4R5]+,
-N H-COR3, -COOH , -COOR3, -CON H2, -CON H R3, -CON R3R4, -CO-H , -COR3, Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C2-3o-alkenyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents R'"; wherein
R3, R4 and R5 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C2-3o-alkenyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents RiH,
R' at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -N3, -OH, Ci-30-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR3, -S-Ci-so-alkyl, -SO2-Ci-30-alkyl, -NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR6, -COOH, -COOR6, -CONH2, -CONHR6, -CONR6R7, -CO-H, -COR6, C3-io-cycloalkyl, and C6-i4-aryl,
R" at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -OH, Ci-30-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR6, -S-Ci-30-alkyl, -NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR6, -COOH, -COOR6, -CONH2, -CONHR6, -CONR6R7, - CO-H, -COR6, Ci-3o-alkyl, C2-3o-alkenyl, C3-io-cycloalkyl, and C6-i4-aryl,
RiN at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -N3, -OH, Ci-3o-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR6, -S-Ci-30-alkyl, -SO2-Ci-30-alkyl, -NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR6, -COOH, -COOR6, -CONH2, -CONHR6, -CONR6R7, -CO-H, -COR6, Ci-30-alkyl, C2-30-alkenyl, C3-io-cycloalkyl, and C6-i4-aryl, wherein
R6, R7 and R8 at each occurrence are independently from each other selected from the group consisting of Ci-3o-alkyl, C2-3o-alkenyl, C3-io-cycloalkyl, and C6-i4-aryl, and
X is -CI, -Br or I.
More preferably,
R1 and R2 are independently from each other Ci-3o-alkyl optionally substituted with 1 to 30 substituents Ra, wherein
Ra at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -N3, -OH, Ci-3o-alkoxy optionally substituted with 1 to 6 substituents R, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10),
-O-COR3, -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R', -SO2-Ci-30-alkyl optionally substituted with 1 to 30 substituents R', -NH2, -NHR3, -NR3R4, -[NR3R4R5]+, -NH-COR3, -COOH, -COOR3, -CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, C3-io-cyclo- alkyl optionally substituted with 1 to 10 substituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents R'"; wherein
R3, R4 and R5 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C2-3o-alkenyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents RiH,
R' at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -N3, -OH, Ci-30-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR3, -S-Ci-so-alkyl, -NH2, -NHR6, -SO2-Ci-30-alkyl, -NR6R7, -[NR6R7R8]+, -NH-COR6, -COOH, -COOR6, -CONH2, -CONHR6, -CONR6R7, -CO-H, -COR6, C3-io-cycloalkyl, and C6-i4-aryl,
R" at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -OH, Ci-30-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR6, -S-Ci-30-alkyl, -NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR6, -COOH, -COOR6, -CONH2, -CONHR6, -CONR6R7, - CO-H, -COR6, Ci-3o-alkyl, C2-3o-alkenyl, C3-io-cycloalkyl, and C6-i4-aryl,
RiN at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -N3, -OH, Ci-3o-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR6, -S-Ci-30-alkyl, -SO2-Ci-30-alkyl, -NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR6, -COOH, -COOR6, -CONH2, -CONHR6, -CONR6R7, -CO-H, -COR6, Ci-30-alkyl, C2-30-alkenyl, C3-io-cycloalkyl, and C6-i4-aryl, wherein
R6, R7 and R8 at each occurrence are independently from each other selected from the group consisting of Ci-3o-alkyl, C2-3o-alkenyl, C3-io-cycloalkyl, and C6-i4-aryl, and
X is -CI, -Br or -I. Most preferably,
R1 and R2 are independently from each other C3-25-alkyl branched at the C attached to the N of formula 1 and
X is -CI, -Br or -I. Particular preferred are the compounds of formulae
and
Also part of the invention, is a process for the preparation of the compound of formula 1
wherein R1 and R2 are as defined above, which process comprises the steps of
(i) treating a compound of formula (2) with a boron-containing compound of formula (3) in the presence of a transition metal-containing catalyst to form a boron-containing compound of formula (4)
wherein R1 and R2 are as defined above, and L is a linking group, and
(ii) treating the boron-containing compound of formula (4) with a CI-, Br- or l-source in order to form the compound of formula (1 ).
L is preferably C2-5-alkylene, which can be optionally substituted with 1 to 6 Ci-10-alkyl groups. More preferably L is ethylene or propylene and is substituted with 2 to 4 methyl groups. The transition metal-containing catalyst can be an iridium-containing catalyst such as
[lr(cod)OMe]2, or, preferably, a ruthenium-containing catalyst, such as RuH2(CO)(PPh3)3.
If the transition metal-containing catalyst is an iridium-containing catalyst, the first step can be performed in the presence of a base such as di-feri-butylbipyridine. If the transition metal- containing catalyst is an iridium-containing catalyst, the first step is usually performed in a suitable organic solvent such as tetrahydrofuran or 1 ,4-dioxane. If the transition metal-containing catalyst is an iridium-containing catalyst, the first step is usually performed at elevated temperatures, such as at temperatures from 60 to 1 10 °C. In principal, if the transition metal-containing catalyst is an iridium-containing catalyst, the first step can be performed in analogy to the method described by C. W. Liskey; X. Liao; J. F. Hartwig in J. Am. Chem. Soc. 2010, 132, 1 1389- 1 1391 , and by I. A. I. Mkhalid, J. H. Barnard, T. B. Marder, J. M. Murphy and J. F. Hartwig in Chem. Rev. 2010, 110, 890-931 .
If the transition metal-containing catalyst is a ruthenium-containing catalyst, the first step is usu- ally performed in a suitable organic solvent such as toluene, pinacolone and mesitylene or mixtures thereof. If the transition metal-containing catalyst is ruthenium-containing catalyst, the first step is usually performed at elevated temperatures, such as at temperatures from 120 to 160 °C. The Cl-source source can be Cu(ll)Cl2. The Br-source source can be Cu(ll)Br2. The l-source source can be Nal in combination with chloroamine T.
The second step is usually performed in a suitable solvent such as water, methanol, THF and dioxane, or mixtures thereof. The second step is usually performed at elevated temperatures, such as at temperatures from 40 to 140 °C. When Cu(ll)Cl2 and Cu(ll)Br2 are used, the second step is preferably performed at elevated temperatures, such as at temperatures from 80 to 140 °C. When Nal in combination with chloroamine T is used, the second step is preferably performed at elevated temperatures, such as at temperatures from 40 to 80 °C.
The compounds of formulae (4) and (1 ) can be isolated by methods known in the art, such as column chromatography.
The compound of formula (2) can be obtained by methods known in the art, for example as described in the subsection titled "Synthesis" of F. Wurthner, Chem. Commun., 2004, 1564-1579. Also part of the present invention is an electronic device comprising the compound of formula (1 ) as semiconducting material. Preferably, the electronic device is an organic field effect transistor (OFET).
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 an organic field-effect transistor is the bottom-gate design. Examples of bottom-gate designs are shown in Figures 1.
Another design of an organic field-effect transistor is the top-gate design. Examples of top-gate designs are shown in Figure 2.
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 silicon dioxide, or, an organic polymer such as polystyrene (PS), poly(methylmethacrylate) (PMMA), poly(4-vinylphenol) (PVP), polyvinyl alcohol) (PVA), benzocyclobutene (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 electrodes can be made from any suitable source/drain material, for example 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, gold (Au) and/or tantalum (Ta). The gate elec- trode can have a thickness of 1 to 200 nm, preferably from 5 to 100 nm.
The substrate can be any suitable substrate such as glass, or a plastic substrate such as poly- ethersulfone, polycarbonate, polysulfone, polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). Depending on the design of the organic field effect transistor, a combination of the gate electrode and the dielectric layer can also function as substrate.
The organic field effect transistor can be prepared by methods known in the art.
For example, a bottom-gate organic field effect transistor can be prepared as follows:
The gate electrode can be formed by depositing the gate material, for example highly doped silicon, on one side of the dielectric layer made of a suitable dielectric material, for example si- licium dioxide. The other side of the dielectric layer can be optionally treated with a suitable reagent, for example with hexamethyldisilazane (HMDS). Source/drain electrodes can be deposited on this side (the side which is optionally treated with a suitable reagent) of the dielectric layer for example by vapour deposition of a suitable source/drain material, for example tantalum (Ta) and/or gold (Au). The source/drain electrodes can then be covered with the semiconducting layer by solution processing, for example drop coating, a solution of the semiconducting material of the present invention in s suitable solvent, for example in chloroform. Also part of the invention is the use of the compound of formula (1 ) as semiconducting material.
In Figure 1 two designs of a bottom-gate organic field effect transistor are shown. In Figure 2 two designs of a top-gate organic field effect transistor are shown.
In Figure 3 the bottom-gate organic field effect transistor of example 6 is shown.
In Figure 4 the drain current ISD [A] in relation to the gate voltage VSG [V] (top transfer curve) and the drain current ISD0 5 [μΑ0 5] in relation to the gate voltage VSG [V] (bottom transfer curve) for the bottom-gate organic field effect transistor of example 6 comprising compound 1c as semiconducting material at a drain voltage VSD of 100 V is shown. In Figure 5 the drain current ISD [A] in relation to the drain voltage VSD [V] (output curve) for the bottom-gate organic field effect transistor of example 6 comprising compound 1c as semiconducting material at a gate voltage VSG of 100 V (first and top curve), 90 V (second curve), 80 V (third curve), 70 V (fourth curve) and 0 V (fifth and bottom curve) is shown.
In Figure 6 the drain current ISD [A] in relation to the gate voltage VSG [V] (top transfer curve) and the drain current ISD0 5 [μΑ0 5] in relation to the gate voltage VSG [V] (bottom transfer curve) for the bottom-contact organic field effect transistor of example 6 comprising compound 1 b as semiconducting material at a drain voltage VSD of 100 V is shown.
In Figure 7 the drain current ISD [A] in relation to the drain voltage VSD [V] (output curve) for the bottom-gate organic field effect transistor of example 6 comprising compound 1 b as semiconducting material at a gate voltage VSG of 100 V (first and top curve), 90 V (second curve), 80 V (third curve), 0 V (fourth and bottom curve) is shown.
In Figure 8 the charge carrier mobility μ33ι [cmWs] in relation to the gate voltage VSG [V] for the bottom-gate organic field effect transistor of example 6 comprising compound 1c as semiconducting material is shown. In Figure 9 the charge carrier mobility μ33ι [cmWs] in relation to the gate voltage VSG [V] for the bottom-gate organic field effect transistor of example 6 comprising compound 1 b as semiconducting material is shown.
The advantage of the semiconducting materials of the present invention is the high solubility of these materials in solvents suitable for solution processing. In addition the semiconducting materials of the present invention show acceptable to high charge carrier mobility. In addition, the semiconducting materials are stable, in particular towards oxidation, under ambient conditions.
Examples
Example 1
Preparation of A/,A/'-bis(1 -ethylpropyl)-2,5,8,1 1 -tetrakis[4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2- yl]perylene-3,4:9,10-tetracarboxylic acid bisimide (4a)
(2a) (4a) A/,A/'-Bis(1 -ethylpropyl) perylene-3,4:9,10-tetracarboxylic acid bisimide (2a) (100 mg,
0.189 mmol) and bispinacolonediboronate (3a) (0.383 g, 1.51 mmol) are mixed together and dissolved in 2 ml. dry mesitylene and 0.15 ml. dry pinacolone. Argon is bubbled trough the solution for 30 minutes. RuH2(CO)(PPh3)3 (0.082 mg, 0.09 mmol) is added to the reaction mixture and the vessel heated to 140°C for 30 hours. After cooling the system to room temperature, the solvent is evaporated and the desired compound purified by column chromatography (silica, CH2CI2/AcOEt 50/1 ). An orange bright solid is obtained with 60% yield (1 17 mg, 0.1 13 mmol). H NMR (250 MHz, CD2CI2) δ 8.59 (s, J = 1.2, Hz, 4H), 4.94 (tt, J = 9.2, 6.0 Hz, 2H), 2.33 - 2.10 (m, 4H), 2.04 - 1 .84 (m, 4H), 1 .51 (s, J = 7.2 Hz, 48H), 0.92 (t, J = 7.4 Hz, 12H). FD Mass Spec- trum (8kV): m/z= 1033.33 (100%) [M+]. Absorption: 537 nm (in toluene). Emission: 548 nm (in toluene, exc 537 nm). Extinction Coefficient: 7.30 X 104 M-1cnr1. Fluorescence Quantum Yield: 0.89. Elemental Analysis: theoretical: C: 67.34%; H: 7.21 %; N: 2.71 %; experimental: C: 67.29%; H: 7.40%; N: 2.96%. Example 2
Preparation of A/,A/'-Bis(1 -ethylpropyl)-2,5,8,1 1 -tetrabromo-perylene-3,4:9,10-tetracarboxylic acid bisimide (1a)
(4a) (1a)
A/,A/'-Bis(1 -ethylpropyl)-2,5,8,1 1 -tetrakis[4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-y]perylene- 3,4:9,10-tetracarboxylic acid bisimide (4a), prepared as described in example 1 , (400 mg, 0.387 mmol) and copper(ll) bromide (1.73 g, 7.73 mmol) are suspended in a mixture of methanol (3 ml.) and water (3 ml.) and heated at 100 °C for 6 hours. The reaction mixture is then poured in water and extracted with dichloromethane. The organic phase is dried over magnesium sulfate and the solvent evaporated. The compound 1a is obtained as an orange solid after column chromatography (silica, dichloromethane) in 90% yield (295 mg, 0.39 mmol). H NMR (250 MHz, CD2CI2) δ 8.71 (s, 4H), 4.95 (m, 2H), 2.23 - 2.02 (m, 4H), 1.97 - 1.78 (m, 4H), 0.84 (t, J = 7.5 Hz, 12H). FD Mass Spectrum (8kV): m/z= 844.8 (100%) [M+].
Example 3
Preparation of A/,A/'-bis(1 -heptyloctyl)-2,5,8,1 1 -tetrakis[4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2- yl]perylene-3,4:9,10-tetracarboxylic acid bisimide (4b)
A/,A/'-Bis(1 -heptyloctyl) perylene-3,4:9,10-tetracarboxylic acid bisimide (2b) (100 mg, 0.12 mmol) and bispinacolonediboronate (3a) (250 mg, 0.99 mmol) are mixed together and dissolved in 1 ml. anhydrous mesitylene and 1 ml. anhydrous pinacolone. Argon is bubbled through the solution for 30 minutes. RuH2(CO)(PPh3)3 (23 mg, 0,03 mmol) is added to the mixture and the reaction mixture is heated at 140°C for 30 hours. After cooling the system to room temperature, the solvent is evaporated and the desired compound purified by column chromatography (CH2CI2). 4b is obtained as a red solid in 70% yield (1 13 mg, 0.09 mmol). H NMR (250 MHz, CD2CI2) δ 8.58 (s, 4H), 5.06 (s, 2H), 2.35 - 2.06 (m, 4H), 1.98 - 1.72 (m, 4H), 1 .50 (s, 48H), 1 .24 (s, 40H), 0.84 (t, J = 6.5 Hz, 12H). 3C NMR (126 MHz, CD2CI2) δ 166.27 (d, J = 98.5 Hz), 139.79 - 138.86 (m), 133.80 (s), 128.82 (s), 127.57 (d, J = 69.0 Hz), 127.30 (s), 126.29 (s), 84.90 (s), 55.19 (s), 32.83 (s), 32.45 (s), 30.03 (s), 29.76 (s), 27.37 (s), 25.38 (s), 23.22 (s), 14.43 (s). FD/MS (8kV): m/z= 1312.4 (100%) [M+]. UV-Vis(in toluene):
Amax(e[M-1cm-1]): 538 nm (5,57 X 104). Fluorescence (in toluene, Aex= 538 nm): 548 nm. ΦΡ: 0.83. Elem. Anal.: theoretical: C: 71.24%; H: 8.74%; N: 2.13%; experimental: C: 70.76%; H: 8.27%; N: 2.50%. Example 4
Preparation of A/,A/'-Bis(1 -heptyloctyl)-2,5,8,1 1 -tetrachloro-perylene-3,4:9,10-tetracarboxylic acid bisimide (1 b)
(4b) (1b)
A/,A/'-Bis(1 -heptyloctyl)-2,5,8,1 1 -tetrakis[4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-y]perylene- 3,4:9,10-tetracarboxylic acid bisimide (4b), prepared as described in example 3, (1 .00 g, 0.76 mmol) and copper(ll) chloride (1 .23 g, 9.13 mmol) are suspended in a mixture of methanol (3 mL) and water (3 mL) and heated in a closed vessel at 100 °C for 6 hours. The reaction mixture is then poured in water and extracted with dichloromethane. The organic phase is dried over magnesium sulfate and the solvent evaporated. The compound 1 b is obtained as an orange solid after column chromatography (silica, dichloromethane) in 87% yield (0.628 g, 0.66 mmol). H NMR (250 MHz, CD2CI2) δ 8.43 (s, 4H), 5.06 (m, 2H), 2.22 - 1 .99 (m, 4H), 1 .79 (m, 4H), 1 .20 (m, 40 H), 0.82 - 0.69 (m, 12H). FD Mass Spectrum (8kV): m/z= 947.7 (100%) [M+]. Example 5
Preparation of A/,A/'-Bis(1 -heptyloctyl)-2,5,8,1 1 -tetrabromo-perylene-3,4:9,10-tetracarboxylic acid bisimide (1c)
(4b) (1c)
A/,A/'-Bis(1 -heptyloctyl)-2,5,8,1 1 -tetrakis[4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-y]perylene- 3,4:9,10-tetracarboxylic acid bisimide (4b), prepared as described in example 3, (1 .00 g, 0.76 mmol) and copper(ll)-bromide (3.39 g, 15.20 mmol) are suspended in 80 ml. of a 1/1/1 mixture of dioxane/methanol/water and heated at 120°C for 12 hours. The reaction mixture is then cooled, poured in water and extracted with dichloromethane. The organic phase is dried over magnesium sulfate and the solvent is evaporated. Compound 1c is obtained as an orange solid after column chromatography (silica, dichloromethane: petrol ether 1 :1 ) in 92% yield (0.79 g, 0.70 mmol). H NMR (500 MHz, CD2CI2) δ 8.74 (s, 4H), 5.22 - 5.07 (m, 2H), 2.19 (m, 4H), 1.88 (m, 4H), 1 .39 - 1.18 (m, 40H), 0.84 (t, J= 6.3 Hz, 12H). 3C NMR (126 MHz, CD2CI2) δ 161 .65 (s), 133.1 1 (s), 132.76 (s), 132.05 (s), 129.36 (s), 125.15 (s), 122.07 (s), 56.26 (s), 32.80 (s), 32.37 (s), 30.03 (s), 29.78 (s), 27.52 (s), 23.20 (s), 14.41 (s). FD/MS (8kV): m/z = 1 124.8
(100%) [M+]. UV-Vis (in dichloromethane): max (ε [M-1cnr1]): 509 nm (7.9 x 104). Fluorescence (in dichloromethane, λβχ = 509 nm): 519 nm. ΦΡ: 0.21. Elem. Anal.: theoretical: C: 57.56%; H: 5.90%; N: 2.49%; experimental: C: 57.25%; H: 6.27%; N: 2.52%. Example 6
Preparation of bottom-gate organic field effect transistors containing compound 1 b, respectively, 1c as semiconducting material Thermally grown silicon dioxide (thickness: 200 nm) is used as dielectric layer. The gate electrode is formed by depositing highly doped silicon on one side of the dielectric layer. The other side of the dielectric layer is treated with hexamethyldisilazane (HMDS) by vapour deposition of hexamethyldisilazane. The contact angle of the surface of the HMPS-treated side of the dielectric layer is 93.2 ± 1.3°. Source/drain electrodes (Ta (thickness: 10 nm) covered by Au (thick- ness: 40 nm)) are deposited on the HMPS-treated side of the dielectric layer by vapour deposition. The channel length is 20 μηη and the channel width is 1.4 mm, affording W/L = 70. The source/drain electrodes are then covered with the semiconducting layer (thickness: ca. 100 nm) by drop-casting a solution of compound 1 b, respectively, 1c in chloroform (concentration = 10 mg/mL) in a nitrogen filled glove box (O2 content: 0.1 ppm, H2O content: 0.0 ppm, pressure: 1 120 Pa, temperature: 17 °C) using a Keithley 4200 machine.
The design of the bottom-gate organic field effect transistor of example 6 is shown in Figure 3.
The drain current ISD [A] in relation to the gate voltage VSG [V] (top transfer curve) and the drain current ISD0 5 [μΑ° 5] in relation to the gate voltage VSG [V] (bottom transfer curve) for the bottom- gate organic field effect transistor of example 6 comprising compound 1c as semiconducting material at a drain voltage VSD of 100 V is determined in a nitrogen filled glove box (O2 content: 0.1 ppm, H20 content: 0.0 ppm, pressure: 1 120 Pa, temperature: 17 °C) using a Keithley 4200 machine is shown. The results are shown in Figure 4.
The drain current ISD in relation to the drain voltage VSD (output curve) for the bottom-gate organic field effect transistor of example 6 comprising compound 1c as semiconducting material at a gate voltage VSG of 100 V (first and top curve), 90 V (second curve), 80 V (third curve), 70 V (fourth curve) and 0 V (fifth and bottom curve) is determined in a nitrogen filled glove box (O2 content: 0.1 ppm, H2O content: 0.0 ppm, pressure: 1 120 Pa, temperature: 17 °C) using a Keithley 4200 machine is shown. The results are shown in Figure 5.
The drain current ISD [A] in relation to the gate voltage VSG [V] (top transfer curve) and the drain current ISD0 5 [μΑ° 5] in relation to the gate voltage VSG [V] (bottom transfer curve) for the bottom- gate, organic field effect transistor of example 6 comprising compound 1 b as semiconducting material at a drain voltage VSD of 100 V is determined in a nitrogen filled glove box (O2 content: 0.1 ppm, H20 content: 0.0 ppm, pressure: 1 120 Pa, temperature: 17 °C) using a Keithley 4200 machine is shown. The results are shown in Figure 6. The drain current ISD in relation to the drain voltage VSD (output curve) for the bottom-gate organic field effect transistor of example 6 comprising compound 1 b as semiconducting material at a gate voltage VSG of 100 V (first and top curve), 90 V (second curve), 80 V (third curve) and 0 V (fourth and bottom curve) is determined in a nitrogen filled glove box (O2 content: 0.1 ppm, H2O content: 0.0 ppm, pressure: 1 120 Pa, temperature: 17 °C) using a Keithley 4200 machine is shown. The results are shown in Figure 7.
In Figure 8 the charge carrier mobility μ33ι [cmWs] in relation to the gate voltage VSG [V] for the bottom-gate organic field effect transistor of example 6 comprising compound 1c as semiconducting material is shown.
In Figure 9 the charge carrier mobility μ33ι [cmWs] in relation to the gate voltage VSG [V] for the bottom-gate organic field effect transistor of example 6 comprising compound 1 b as semicon- ducting material is shown.
The average values and the 90% confidence interval (in parentheses) of the charge carrier mobilities μ53ι [cmWs], the ION/IOFF ratios and the switch-on voltages Vso [V] for the bottom-gate organic field effect transistors of example 6 comprising compound 1 b, respectively, 1c, as semi- conducting material are given in table 1. The switch-on voltage Vso [V] is the gate voltage VSG [V] where the drain current ISD [A] starts to increase (out of the off-state).
Table 1 .
Example 7
Preparation of A/,A/'-Bis(1 -heptyloctyl)-2,5,8,1 1 -tetraiodo-perylene-3,4:9,10-tetracarboxylic acid bisimide (1d)
(4b) (1d)
A/,A/'-Bis(1 -heptyloctyl)-2,5,8,1 1 -tetrakis[4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-y]perylene- 3,4:9,10-tetracarboxylic acid bisimide (4b), prepared as described in example 3, (100 mg, 0.08 mmol) is suspended in a mixture of 1/1 water/THF (50 ml_). Chloramine T (600 mg, 4.53 mmol) and sodium iodide (680 mg, 4.53 mmol) are added to the mixture. The vessel is sealed and heated at 55 °C for 12 hours without light. After cooling the reaction mixture to room temperature, saturated solution of sodium sulfite (10 ml.) is added. Successively, the reaction mixture is added to water (100 ml_). The solid is filtrated, dried and purified by column chroma- tography (1/1 petrol ether, dichlromethane). The compound 1d is obtained as a red solid in 42% yield. H NMR (700 MHz, CD2CI2) δ 9.10 (s, 4H), 5.22-5.1 1 (m, 2H), 2.26-2.14 (m, 4H), 1 .95-1 .87 (m, 4H), 1 .40-1 .18 (m, 40H), 0.84 (t, J = 7.0 Hz, 12H). 3C NMR (176 MHz, CD2CI2) δ 161 .27 (s), 139.06 (s), 138.60 (s), 132.38 (s), 131 .73 (s), 126.28 (s), 124.09 (s), 56.56 (s), 32.76 (s), 32.38 (s), 30.04 (s), 29.80 (s), 27.52 (s), 32.22 (s), 14.43 (s). FD/MS (8kV): m/z= 1315.4 (100%) [M+]. UV-VIS (in dichloromethane): max (ε [M-1cnr1]): 518 nm (7.23 x 104). Elem. Anal.: theoretical: C: 49.33%; H: 5.06%; N: 2.13%; experimental: C: 49.68%; H: 5.01 %; N: 2.24%. Example 8
Preparation of A/,A/'-Bis-octyl-2,5,8,1 1 -tetrabromo-perylene-3,4:9,10-tetracarboxylic acid bisim- ide (1e)
A/,A/'-Bis-octyl-2,5,8,1 1 -tetrakis[4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-y]perylene-3,4:9,10- tetracarboxylic acid bisimide (0.68 mg, 0.61 mmol) and copper(ll) bromide (1 ,62 g, 7.3 mmol) are suspended in a mixture of dioxane (10 mL), methanol (3 ml) and water (3 ml) and heated at 120°C for 12 hours. The reaction mixture is then poured into HCI (1 .0 M) and the solid so obtained filtered. The desired compound is obtained as an orange solid after column chromatography (silica, dichloromethane) in 30% yield (0.17 mg, 0.18 mmol). H NMR (250 MHz, THF-d8) δ = 9.02 (s, 4H), 4.20 (m, 4H), 1.42 (m,24H), 0.95 (t, J=6.0, 6H). FD Mass Spectrum (8kV): m/z= 932.6 (100%) [M+].
Example 9
Preparation of A/,A/'-Bis-(2-ethylhexyl)-2,5,8,1 1 -tetrabromo-perylene-3,4:9,10-tetracarboxylic acid bisimide (1f)
A/,A/'-Bis-(2-ethylhexyl)-2,5,8,1 1 -tetrakis[4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-y]perylene- 3,4:9,10-tetracarboxylic acid bisimide (0.68 mg, 0.61 mmol) and copper(ll) bromide (1 ,62 g, 7.3 mmol) are suspended in a mixture of dioxane (10 mL), methanol (3 ml) and water (3 ml) and heated at 120 °C for 12 hours. The reaction mixture is then poured into HCI (1 .0 M) and the solid so obtained filtered. The desired compound is obtained as an orange solid after column chromatography (silica, dichloromethane) in 39% yield (0.22 mg, 0.24 mmol). H NMR (250 MHz, Methylene Chloride-d2) δ = 8.56 (s,4H), 4.06 (m, 4H),2.16 (m, 2H), 1.17 (m, 16H), 0.82 (m, 12H). FD Mass Spectrum (8kV): m/z= 932.8 (100%) [M+].

Claims

Claims
. A compound of formula
wherein
R1 and R2 are independently from each other selected from the group consisting of H, Ci-30-alkyl optionally substituted with 1 to 30 substituents Ra, C2-3o-alkenyl optionally substituted with 1 to 30 substituents Ra, C2-3o-alkynyl optionally substituted with 1 to 30 substituents Ra,
C3-io-cycloalkyl optionally substituted with 1 to 10 substituents Rb, Cs-io-cycloalkenyl optionally substituted with 1 to 10 substituents Rb, 3-14 membered cycloheteroalkyi optionally substituted with 1 to 8 substituents Rb, C6-i4-aryl optionally substituted with 1 to 8 substituents Rc and 5-14 membered heteroaryl optionally substituted with 1 to 8 substituents Rc, wherein
Ra at each occurrence are independently from each other selected from the group consisting of halogen, -CN , -NO2, -IM3, -OH , Ci-30-alkoxy optionally substituted with 1 to 6 substitu- ents R', -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10),
-O-COR3, -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R', -S02-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R', -N H2, -N H R3, -N R3R4, -[N R3R4R5]+, -N H-COR3, -COOH , -COOR3, -CON H2, -CON H R3, -CON R3R4, -CO-H , -COR3, C3-io-cyclo- alkyl optionally substituted with 1 to 10 substituents R", Cs-io-cycloalkenyl optionally substi- tuted with 1 to 10 substituents R", 3-14 membered cycloheteroalkyi optionally substituted with 1 to 10 substituents R", C6-i4-aryl optionally substituted with 1 to 8 substituents R'" and 5-14 membered heteroaryl optionally substituted with 1 to 8 substituents R'";
Rb at each occurrence are independently from each other selected from the group consist- ing of halogen, -CN , -NO2, -OH , Ci-30-alkoxy optionally substituted with 1 to 30 substituents
R, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR3, -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R', -N H2, -N H R3, -N R3R4, -[N R3R4R5]+, -N H-COR3, -COOH , -COOR3, -CON H2, -CON H R3, -CON R3R4, -CO-H , -COR3, Ci-3o-alkyl optionally substituted with 1 to 30 substituents R', C2-3o-alkenyl optionally substi- tuted with 1 to 30 substituents R', C2-3o-alkynyl optionally substituted with 1 to 30 substitu- ents R', C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", Cs-io-cycloalkenyl optionally substituted with 1 to 10 substituents R", 3-14 membered cycloheteroalkyi optionally substituted with 1 to 10 substituents R",C6-i4-aryl optionally substituted with 1 to 8 substituents R'" and 5-14 membered heteroaryl optionally substituted with 1 to 8 substituents RiN;
Rc at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -NO2, -IM3, -OH, Ci-30-alkoxy optionally substituted with 1 to 30 substituents -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR3, -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R', -SO2-Ci-30-alkyl optionally substituted with 1 to 30 substituents R', -NH2, -NHR3, -NR3R4, -[NR3R4R5]+, -NH-COR3, -COOH, -COOR3, -CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C2-3o-alkenyl optionally substituted with 1 to 30 substituents R', C2-3o-alkynyl optionally substituted with 1 to 30 substituents R',
C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", Cs-io-cycloalkenyl optionally substituted with 1 to 10 substituents R", 3-14 membered cycloheteroalkyi optionally substituted with 1 to 10 substituents R", C6-i4-aryl optionally substituted with 1 to 8 substituents R'" and 5-14 membered heteroaryl optionally substituted with 1 to 8 substituents R'"; wherein
R3, R4 and R5 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C2-3o-alkenyl optionally substituted with 1 to 30 substituents R', C2-3o-alkynyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", Cs-io-cycloalkenyl optionally substituted with 1 to 10 substituents
R", 3-14 membered cycloheteroalkyi optionally substituted with 1 to 10 substituents R", C6-i4-aryl optionally substituted with 1 to 8 substituents R'" and 5-14 membered heteroaryl optionally substituted with 1 to 8 substituents R'", R' at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -N3, -OH, Ci-30-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR3, -S-Ci-30-alkyl, -SO2-Ci-30-alkyl, -NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR6, -COOH, -COOR6, -CONH2, -CONHR6, -CONR6R7, -CO-H, -COR6, C3-io-cycloalkyl, C5-io-cycloalkenyl, 3-14 membered cyclo- heteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl,
R" at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -OH, Ci-30-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR6, -S-Ci-30-alkyl, -NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR6, -COOH, -COOR6, -CONH2, -CONHR6, -CONR6R7, -
CO-H, -COR6, Ci-3o-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io- cycloalkenyl, 3-14 membered cycloheteroalkyi, C6-i4-aryl and 5-14 membered heteroaryl, RiN at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -NO2, -N3, -OH, Ci-30-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR6, -S-Ci-30-alkyl, -S02-Ci-3o-alkyl, -NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR6, -COOH, -COOR6, -CONH2, -CONHR6,
-CONR6R7, -CO-H, -COR6, Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, C5-io-cycloalkenyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl, wherein
R6, R7 and R8 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, C5-io-cycloalkenyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl,
and
X is -CI, -Br or -I.
2. The compound of claim 1 , wherein
R1 and R2 are independently from each other selected from the group consisting of H, Ci-3o-alkyl optionally substituted with 1 to 30 substituents Ra, C2-3o-alkenyl optionally substituted with 1 to 30 substituents Ra, C3-io-cycloalkyl optionally substituted with 1 to 10 substituents Rb, and C6-i4-aryl optionally substituted with 1 to 8 substituents Rc, wherein
Ra at each occurrence are independently from each other selected from the group consist- ing of halogen, -CN, -N02, -N3, -OH, Ci-3o-alkoxy optionally substituted with 1 to 6 substituents -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10),
-O-COR3, -S-Ci-30-alkyl optionally substituted with 1 to 30 substituents R', -SO2-Ci-30-alkyl optionally substituted with 1 to 30 substituents R', -NH2, -NHR3, -NR3R4, -[NR3R4R5]+, -NH-COR3, -COOH, -COOR3, -CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, C3-io-cyclo- alkyl optionally substituted with 1 to 10 substituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents R'";
Rb at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -OH, Ci-3o-alkoxy optionally substituted with 1 to 30 substituents -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR3,
-S-Ci-30-alkyl optionally substituted with 1 to 30 substituents R', -NH2, -NHR3, -NR3R4, -[NR3R4R5]+, -NH-COR3, -COOH, -COOR3, -CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C2-3o-alkenyl optionally substi- tuted with 1 to 30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to 10 sub- stituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents R'";
Rc at each occurrence are independently from each other selected from the group consist- ing of halogen, -CN, -NO2, -IM3, -OH, Ci-30-alkoxy optionally substituted with 1 to 30 substituents -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR3, -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R', -SO2-Ci-30-alkyl optionally substituted with 1 to 30 substituents R', -NH2, -NHR3, -NR3R4, -[NR3R4R5]+, -NH-COR3, -COOH, -COOR3, -CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, Ci-30-alkyl op- tionally substituted with 1 to 30 substituents R', C2-3o-alkenyl optionally substituted with 1 to
30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents R'"; wherein
R3, R4 and R5 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C2-3o-alkenyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents RiH,
R' at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -N3, -OH, Ci-30-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR3, -S-Ci-30-alkyl, -SO2-Ci-30-alkyl, -NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR6, -COOH, -COOR6, -CONH2, -CONHR6, -CONR6R7, -CO-H, -COR6, C3-io-cycloalkyl, and C6-i4-aryl,
R" at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -OH, Ci-30-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR6, -S-Ci-30-alkyl, -NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR6, -COOH, -COOR6, -CONH2, -CONHR6, -CONR6R7, -
CO-H, -COR6, Ci-3o-alkyl, C2-3o-alkenyl, C3-io-cycloalkyl, and C6-i4-aryl,
RiN at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -N3, -OH, Ci-30-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR6, -S-Ci-30-alkyl, -SO2-Ci-30-alkyl,
-NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR6, -COOH, -COOR6, -CONH2, -CONHR6, -CONR6R7, -CO-H, -COR6, Ci-30-alkyl, C2-3o-alkenyl, C3-io-cycloalkyl, and C6-i4-aryl, wherein
R6, R7 and R8 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C3-io-cycloalkyl, and C6-i4-aryl, and
X is as defined in claim 1.
3. The compound of claim 1 , wherein
R1 and R2are independently from each other Ci-30-alkyl optionally substituted with 1 to 30 sub- stituents Ra, wherein
Ra at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -NO2, -IM3, -OH, Ci-30-alkoxy optionally substituted with 1 to 6 substitu- ents R, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10),
-O-COR3, -S-Ci-3o-alkyl optionally substituted with 1 to 30 substituents R', -SO2-Ci-30-alkyl optionally substituted with 1 to 30 substituents R', -NH2, -NHR3, -NR3R4, -[NR3R4R5]+, -NH-COR3, -COOH, -COOR3, -CONH2, -CONHR3, -CONR3R4, -CO-H, -COR3, C3-io-cyclo- alkyl optionally substituted with 1 to 10 substituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents RiH; wherein
R3, R4 and R5 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl optionally substituted with 1 to 30 substituents R', C2-3o-alkenyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", and C6-i4-aryl optionally substituted with 1 to 8 substituents RiH,
R' at each occurrence are independently from each other selected from the group con- sisting of halogen, -CN, -N02, -N3, -OH, Ci-30-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR3, -S-Ci-30-alkyl, -SO2-Ci-30-alkyl, -NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR6, -COOH, -COOR6, -CONH2, -CONHR6, -CONR6R7, -CO-H, -COR6, C3-io-cycloalkyl, and C6-i4-aryl, R" at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -OH, Ci-30-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR6, -S-Ci-30-alkyl, -NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR6, -COOH, -COOR6, -CONH2, -CONHR6, -CONR6R7, - CO-H, -COR6, Ci-3o-alkyl, C2-3o-alkenyl, C3-io-cycloalkyl, and C6-i4-aryl,
RiN at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -N3, -OH, Ci-30-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR6, -S-Ci-30-alkyl, -SO2-Ci-30-alkyl, -NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR6, -COOH, -COOR6, -CONH2, -CONHR6, -CONR6R7, -CO-H, -COR6, Ci-30-alkyl, C2-3o-alkenyl, C3-io-cycloalkyl, and C6-i4-aryl, wherein R6, R7 and R8 at each occurrence are independently from each other selected from the group consisting of Ci-30-alkyl, C2-3o-alkenyl, C3-io-cycloalkyl, and C6-i4-aryl, and
X is as defined in claim 1 .
4. The compound of claim 1 , wherein
R1 and R2 are independently from each other C3-25-alkyl branched at the C attached to the N of formula 1 , and X is as defined in claim 1 .
5. A process for the preparation of a compound of formula 1
wherein R1, R2 and X are as defined in claim 1 , which process comprises the steps of
(i) treating a compound of formula (2) with a boron-containing compound of formula (3) in the presence of a transition metal-containing catalyst to form a boron-containing compound of formula (4)
(2) (3) (4) wherein R1 and R2 are as defined in claim 1 , and L is a linking group, and
(ii) treating the boron-containing compound of formula (4) with a Br-, CI- or l-source in order to form the compound of formula (1 ).
6. An electronic device comprising the compound of formula (1 ) of any of claims 1 to 4 as semiconducting material.
7. Use of the compound of formula (1 ) of any of claims 1 to 4 as semiconducting material.
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