EP2742111A1 - Fluorinated perylene-based semiconducting materials - Google Patents

Fluorinated perylene-based semiconducting materials

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Publication number
EP2742111A1
EP2742111A1 EP12747919.4A EP12747919A EP2742111A1 EP 2742111 A1 EP2742111 A1 EP 2742111A1 EP 12747919 A EP12747919 A EP 12747919A EP 2742111 A1 EP2742111 A1 EP 2742111A1
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EP
European Patent Office
Prior art keywords
optionally substituted
substituents
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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Application number
EP12747919.4A
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German (de)
French (fr)
Inventor
Thomas GESSER
Helmut Reichelt
Glauco BATTAGLIARIN
Chen Li
Klaus MÜLLEN
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
Original Assignee
BASF SE
Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
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Priority to EP12747919.4A priority Critical patent/EP2742111A1/en
Publication of EP2742111A1 publication Critical patent/EP2742111A1/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Withdrawn legal-status Critical Current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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/18—Ring systems of four 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
    • H10K10/486—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions the channel region comprising two or more active layers, e.g. forming pn heterojunctions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • 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
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • 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]
    • H10K10/464—Lateral top-gate IGFETs comprising only a single gate
    • 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]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate

Definitions

  • Organic semiconducting materials can be used in electronic devices such as organic photovol- taic (OPV) cells, organic field-effect transistors (OFETs) and organic light emitting diodes (OLEDs).
  • OOV organic photovol- taic
  • OFET organic field-effect transistors
  • OLED 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 pro- cessability, 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.
  • 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-ferf-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 substit- uent groups on the perylene can include a long list of substituents, including halogens such as fluorine or chlorine.
  • WO 2007/093643 describes fluorinated rylenetetracarboxylic acid derivatives. Preferred pounds are of formula IBa
  • R a and R b are independently from each other are H or an organic residue.
  • WO 2008/063609 describes a compound having the following formula 1
  • 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.
  • A, B, I, D, E, F, G and H can be independently CH, C-Br or C-CN.
  • WO 2009/024512 describes halogen-containing perylenetetracarboxylic acid derivatives, and in particular compound IBa
  • residues R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 are CI and/or F, wherein 1 or 2 of the residues R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 can be CN, and/or , and wherein 1 of the residues R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 can be H, and
  • R a and R b are independently from each other are H or an organic residue.
  • the perylene-based semiconducting compound of the present invention is of formula
  • 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 , C2-3o-alkynyl optionally substituted with 1 to 30 substituents R a , C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R b , Cs-io-cycloalkenyl option- ally substituted with 1 to 10 substituents R , 3-14 membered cycloheteroalkyl optionally substituted with 1 to 8 substituents R b , C6-i4-aryl optionally substituted with 1 to 8 substituents R c and 5-14 membered heteroaryl 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', 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 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 s , 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 -3o-alkenyl, C 2-3 o-alkynyl, C3-io-cycloalkyl, C5-io-cycloalkenyl, 3-14 membered cycloheteroalkyl , C6-i4-aryl and 5-14 membered heteroaryl.
  • Ci-10-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 2 o), n-docosyl (C 22 ), n-tetracosyl (C 2 4), n-hexacosyl (C 2 s), n-octacosyl (C 2 e) 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- hexyl)heptyl, n-(1-heptyl)octyl, n-(1-octyl)nonyl, n
  • C 2 -3o-alkenyl can be branched or unbranched.
  • Examples of C 2 -3o-alkenyl are vinyl, propenyl, cis-
  • 3- pentenyl 4-pentenyl, 2-methyl-3-butenyl, hexenyl, heptenyl, octenyl, nonenyl and docenyl, linoleyl (Cie), linolenyl (Cie), oleyl (Cie), arachidonyl (C 2 o), and erucyl (C 22 ).
  • C 2 - 3 o-alkynyl can be branched or unbranched.
  • Examples of C 2 - 3 o-alkynyl are ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, heptynyl , octynyl , nonynyl and decynyl, undecynyl , do- g
  • 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.
  • 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 C9-io-aryl such as 1-naphthyl, 2-naphthyl, indenyl, indanyl and tetrahydronaph- thyl, 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 are monocyclic 5 membered heteroaryl containing 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- tom 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 / 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 examples are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, ferf-butoxy, n-pentoxy, neopentoxy, isopentoxy, hexoxy, n-heptoxy, n-octoxy, n-nonoxy, 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.
  • 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', C 2 -3o-alkenyl optionally substituted with 1 to 30 substituents R', C3-io-cycloalkyl option- ally substituted with 1 to 10 substituents R", and Cs-i4-aryl optionally substituted with
  • R s , 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.
  • R 3 , R 4 and R 5 at each occurrence are independently from each other selected from the group consisting of Ci- 3 o-alkyl optionally substituted with 1 to 30 substituents R', C 2 . 3 o-alkenyl optionally substituted with 1 to 30 substituents R', C 3- 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-30-alkyl, C 2 -3o-alkenyl, C3-io-cycloalkyl, and C6-i4-aryl.
  • R 1 and R 2 are independently from each other C3- 2 5-alkyl branched at the C attached to the N of formula 1. Particular preferred is the compound of formula
  • 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 X is CI, Br or I, with a fluoride source.
  • the fluoride source can be an alkali fluoride, such as potassium fluoride.
  • the ratio of molequivalents fluoride source/compound of formula (5) is in the range of 1/1 to 30/1 , preferably in the range of 10/1 to 30/1.
  • the reaction is usually performed at temperatures between 100 °C and 200 °C, preferably between 130 °C to 180 °C.
  • the reaction is usually performed in a sealed reaction vessel.
  • the reaction is usually performed in an aprotic solvent.
  • aprotic solvents are ethers such as dioxane and diglyme (bis(2-methoxyethyl) ether) or mixtures thereof.
  • X is preferably CI.
  • the compounds of formula (5) can be prepared as described by G. Battagliari; C. Li, V. Enkel- mann, K. Mullen Org. Lett. 2011 , 13, 3012-3015, and G. Battagliari; Y. Zhao; C. Li, K. Mullen Org. Lett. 2011 , 13, 3399-3401.
  • the compounds of formula (1 ) can be isolated by methods known in the art, such as column chromatography.
  • an electronic device comprising the compound of formula (1 ) as semiconducting material.
  • the electronic device is an organic field effect transistor (OFET).
  • OFET organic field effect transistor
  • 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.
  • bottom-gate design 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 electrode 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 charge carrier mobility.

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  • Optics & Photonics (AREA)
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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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  • Thin Film Transistor (AREA)

Abstract

The present invention provides a compound of formula (1). The compound of formula (1) is suitable for use as semiconducting material, in particular in electronic devices.

Description

Fluorinated Perylene-based Semiconducting Materials
Description
Organic semiconducting materials can be used in electronic devices such as organic photovol- taic (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 pro- cessability, 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.
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
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 7,355,198 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-ferf-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 substit- uent groups on the perylene can include a long list of substituents, including halogens such as fluorine or chlorine.
WO 2007/093643 describes fluorinated rylenetetracarboxylic acid derivatives. Preferred pounds are of formula IBa
wherein 1 , 2, 3, 4, 5 or 6 of the residues R11, R12, R13, R14, R21, R22, R23 and R24 are F, optionally at least one of the residues R11, R12, R13, R14, R21, R22, R23 and R24, which is not F, can independently be CI or Br, and the remaining residues are H, and
Ra and Rb are independently from each other are H or an organic residue. WO 2008/063609 describes a compound having the following formula 1
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. For example, A, B, I, D, E, F, G and H can be independently CH, C-Br or C-CN.
WO 2009/024512 describes halogen-containing perylenetetracarboxylic acid derivatives, and in particular compound IBa
wherein the residues R11, R12, R13, R14, R21, R22, R23 and R24 are CI and/or F, wherein 1 or 2 of the residues R11, R12, R13, R14, R21, R22, R23 and R24 can be CN, and/or , and wherein 1 of the residues R11, R12, R13, R14, R21, R22, R23 and R24 can be H, and
Ra and Rb are independently from each other are H or an organic residue.
G. Battagliari; C. Li, V. Enkelmann, K. Mullen Org. Lett. 2011 , 13, 3012-3015 describe compounds of formula
G. Battagliari; Y. Zhao; C. Li, K. Mullen Org. Lett. 2011 , 13, 3399-3401 describe compounds of formulae
So far, it has not been possible to prepare 2,5,8,1 l-tetrafluoroperylene-bis(dicarboximides).
It was the object of the present invention to provide 2,5,8,11 -tetrafluoroperylene- bis(dicarboximides). The object is solved by the compound of claim 1 , the process of claim 5, and the electronic d vice of claim 6.
The perylene-based semiconducting compound of the present invention is 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 option- ally substituted with 1 to 10 substituents R , 3-14 membered cycloheteroalkyl 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, -N3, -OH, Ci-30-alkoxy optionally substituted with 1 to 6 substituents Ri -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', -NH2, -NHR3, -NR3R4, -[NR3R4R5]+,
-NH-COR3, -COOH, -COOR3, -CON H2, -CONHR3, -CONR3R4, -CO-H, -COR3, C3-io-cyclo- alkyl optionally substituted with 1 to 10 substituents R", Cs-io-cycloalkenyl optionally substituted with 1 to 10 substituents R", 3-14 membered cycloheteroalkyl 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 RHi;
R 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 Ri, -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, -NH 3, -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 substitu- ents R', C3-io-cycloalkyl optionally substituted with 1 to 10 substituents R", C5-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, -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, -S02-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-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", C5-io-cycloalkenyl option- ally 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, -NO2, -N3, -OH, Ci-30-alkoxy, -O-[CH2CH2O]n-Ci-i0-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-COR5, -COOH, -COOR6, -CONH2, -CONHR6, -CONR6R7, -CO-H, -COR6, C3-io-cycloalkyl, C5-io-cycloalkenyl, 3-14 membered cycloheteroalkyi, 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, -O-[CH2CH2O]n-Ci-i0-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-CO 6, -S-Ci-3o-alkyl, -NH2, -NH 5, -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 het- eroaryl,
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-COR5, -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
Rs, 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.
Ci-10-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 (C2o), n-docosyl (C22), n-tetracosyl (C24), n-hexacosyl (C2s), n-octacosyl (C2e) 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, n-(1- 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 (Cie), linolenyl (Cie), oleyl (Cie), arachidonyl (C2o), 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- g
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
C5-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 C9-io-aryl such as 1-naphthyl, 2-naphthyl, indenyl, indanyl and tetrahydronaph- thyl, 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 containing 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- tom 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 / 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, phthalazi- nyl, 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, ferf-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, -N3, -OH, O-30-alkoxy optionally substituted with 1 to 6 substitu- ents Ri -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', -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 RHi;
R 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 Ri, -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', 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, -S02-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-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 option- ally substituted with 1 to 10 substituents R", and Cs-i4-aryl 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, -O-[CH2CH2O]n-Ci-i0-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR3, -S-C1-3o-alkyl, -SO2-Ci-30-alkyl,
-NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR5, -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-ao-alkyl, -NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR5, -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-3o-alkyl, -SO2-Ci-30-alkyl,
-NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR6, -COOH, -COOR6, -CONH2, -CONHR6, -CONR6R7, -CO-H, -COR6, Ci-3o-alkyl, C2.30-alkenyl, C3-io-cycloalkyl, and Ce-n-aryl, wherein
Rs, 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.
More preferably,
R1 and R2 are independently from each other Ci-3o-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, -N02, -N3, -OH, Ci-3o-alkoxy optionally substituted with 1 to 6 substitu- ents Ri, -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-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 RiH,
R' at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -N3, -OH, Ci-30-alkoxy, -O-[CH2CH2O]n-Ci-i0-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR3, -S-Ci-3o-alkyl, -NH2, -NHR5, -S02-Ci-3o-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-3o-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-0H (m = 1 to 10), -O-COR6, -S-Ci-3o-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, C2.30-alkenyl, C3-io-cycloalkyl, and Ce-n-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.
Most preferably,
R1 and R2 are independently from each other C3-25-alkyl branched at the C attached to the N of formula 1. Particular preferred is the compound of formula
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 (5)
wherein R1 and R2 are as defined above, and X is CI, Br or I, with a fluoride source.
The fluoride source can be an alkali fluoride, such as potassium fluoride. Usually the ratio of molequivalents fluoride source/compound of formula (5) is in the range of 1/1 to 30/1 , preferably in the range of 10/1 to 30/1. The reaction is usually performed at temperatures between 100 °C and 200 °C, preferably between 130 °C to 180 °C. The reaction is usually performed in a sealed reaction vessel.
The reaction is usually performed in an aprotic solvent. Preferred aprotic solvents are ethers such as dioxane and diglyme (bis(2-methoxyethyl) ether) or mixtures thereof. X is preferably CI.
The compounds of formula (5) can be prepared as described by G. Battagliari; C. Li, V. Enkel- mann, K. Mullen Org. Lett. 2011 , 13, 3012-3015, and G. Battagliari; Y. Zhao; C. Li, K. Mullen Org. Lett. 2011 , 13, 3399-3401.
The compounds of formula (1 ) can be isolated by methods known in the art, such as column chromatography.
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 electrode 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.
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 charge carrier mobility.
Examples
Example 1
Preparation of /V,/V'-bis(1-heptyloctyl)-2, 5,8,11-tetrakis[4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2- yl]perylene-3,4:9,10-tetracarboxylic acid bisimide (4a)
/V,/V'-Bis(1-heptyloctyl) perylene-3,4:9,10-tetracarboxylic acid bisimide (2a) (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). 4a is obtained as a red solid in 70% yield (113 mg, 0.09 mmol).
1 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). 13C 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( [M-1cm-1]): 538 nm (5,57 X 104). Fluorescence (in toluene, Aex= 538 nm): 548 nm. <DF: 0.83. Elem. Anal.: theoretical: C: 71.24%; H : 8.74%; N: 2.13%; experimental: C: 70.76%; H: 8.27%; N: 2.50%.
/V,/V'-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 (4a), prepared as described in example 1 , (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 5a 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 3
Preparation of /V,/V'-Bis(1-heptyloctyl)-2,5,8,11 -tetrafluoro-perylene-3,4:9,10-tetracarboxylic acid bisimide (1a)
/V,/V'-Bis(1-heptyloctyl)-2,5,8,1 1 -tetrachloro-perylene-3,4:9,10-tetracarboxylic acid bisimide (5a), prepared as described in example 2, (50 mg, 0.05 mmol) and potassium fluoride (61 mg, 1.05 mmol) are suspended in a mixture of dioxane (2 ml_) and diglyme(1 ml_) and heated in a sealed vessel at 150 °C for 20 hours in a microwave oven. The reaction mixture is then cooled down, the solvent is removed and the remaining solid is purified by column chromatography (silica gel, dichloromethane/petrol ether 2/1 ). The compound 1a is obtained as a yellow solid in 30% yield (13 mg, 002 mmol). H NMR (250 MHz, CD2CI2) δ 8.23 (d, J = 12.4 Hz, 4 H), 5.15 (m, 2H), 2.18 (m, 4H), 1.82 (m, 4H), 1.25 (m, 40 H), 0.92 - 0.73 (m, 12H). FD Mass Spectrum (8kV): m/z= 947.7 (100%) [M+]. UV-VIS (in dichloromethane): ληΐ3χ: 500 nm. Fluorescence (in dichloromethane, ληΐ3χ: 500 nm): 509 nm.

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 R , C5-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, -N3, -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 -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", 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 RiH 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 consist- ing of halogen, -CN, -N02, -OH, Ci-30-alkoxy optionally substituted with 1 to 30 substituents
Ri, -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 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", C5-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 RiH and 5-14 membered heteroaryl optionally substituted with 1 to 8 substituents Ri";
Rc at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -NO2, -N3, -OH, O-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-30-alkyl optionally substituted with 1 to 30 substituents R, -S02-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-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]„-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR3, -S-C1-3o-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-C1-3o-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, -N02, -N3, -OH, d-30-alkoxy, -0-[CH2CH20]n-Ci-io-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR6, -S-Ci-3o-alkyl, -SO2-Ci-30-alkyl, -NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR5, -COOH, -COOR6, -CONH2, -CONHR6,
-CONR6R7, -CO-H, -COR6, Ci-3o-alkyl, C2.30-alkenyl, C2-30-alkynyl, C3-io-cycloalkyl, C5-io-cycloalkenyl, 3-14 membered cycloheteroalkyl, Ce-14-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.
2. The compound of claim 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, C3-io-cycloalkyl optionally substituted with 1 to 10 substituents Rb, and Ce-14-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 Ri, -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'";
R 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 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\ -NH2, -NHR3, -NR3R4, -[NR3R R5]+, -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\ C3-io-cycloalkyl optionally substituted with 1 to 10 substit- uents 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-3o-alkoxy optionally substituted with 1 to 30 substit- uents 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 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-0H (m = 1 to 10), -O-COR3, -S-Ci-3o-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-3o-alkoxy, -O-[CH2CH2O]n-Ci-i0-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR6, -S-Ci-3o-alkyl, -NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR5, -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-so-alkyl, -SO2-Ci-30-alkyl,
-NH2, -NHR6, -NR6R7, -[NR6R7R8]+, -NH-COR5, -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.
3. The compound of claim 1 , wherein
R1 and R2 are 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 Ri -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, -N 3R4, -[NR3R4R5]+,
-NH-COR3, -COOH, -COOR3, -CON H2, -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 R'",
R' at each occurrence are independently from each other selected from the group consisting of halogen, -CN, -N02, -N3, -OH, Ci-30-alkoxy, -O-[CH2CH2O]n-Ci-i0-alkyl (n = 1 to 10), -0-[CH2CH20]m-OH (m = 1 to 10), -O-COR3, -S-Ci-30-alkyl, -S02-Ci-3o-alkyl, -NH2, -NHR6, -N R6R7, -[NR6R7R8]+, -NH-COR5, -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-COR5, -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, d-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
R5, 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.
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.
5. A process for the preparation of a compound of formula
wherein R1 and R2 are as defined in claim 1 , which process comprises the step of
(i) treating a compound of formula
R
o^isk^o
wherein R1 and R2 are as defined in claim 1 , and X is CI, Br or I, with a fluoride source.
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.
EP12747919.4A 2011-08-12 2012-08-10 Fluorinated perylene-based semiconducting materials Withdrawn EP2742111A1 (en)

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US201161522705P 2011-08-12 2011-08-12
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EP12747919.4A EP2742111A1 (en) 2011-08-12 2012-08-10 Fluorinated perylene-based semiconducting materials
PCT/EP2012/065684 WO2013024026A1 (en) 2011-08-12 2012-08-10 Fluorinated perylene-based semiconducting materials

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EP2742112B1 (en) 2011-08-12 2016-05-18 Basf Se Carbazolocarbazol-bis(dicarboximides) and their use as semiconductors
EP2960280A1 (en) * 2014-06-26 2015-12-30 E.T.C. S.r.l. Photocrosslinkable compositions, patterned high k thin film dielectrics and related devices
CN109153772B (en) * 2016-05-25 2022-05-03 Clap有限公司 Semiconductor device and method for manufacturing the same
JP7464397B2 (en) * 2020-01-31 2024-04-09 保土谷化学工業株式会社 Perylene derivative compound, organic semiconductor composition using said compound, and organic thin film transistor using said organic semiconductor composition

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US7326956B2 (en) 2004-12-17 2008-02-05 Eastman Kodak Company Fluorine-containing N,N′-diaryl perylene-based tetracarboxylic diimide compounds as N-type semiconductor materials for thin film transistors
EP1987092B1 (en) 2006-02-17 2013-05-22 Basf Se Fluorinated rylenetetracarboxylic acid derivatives and use thereof
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