WO2012117089A1 - Perylene-based semiconducting materials - Google Patents

Perylene-based semiconducting materials Download PDF

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Publication number
WO2012117089A1
WO2012117089A1 PCT/EP2012/053605 EP2012053605W WO2012117089A1 WO 2012117089 A1 WO2012117089 A1 WO 2012117089A1 EP 2012053605 W EP2012053605 W EP 2012053605W WO 2012117089 A1 WO2012117089 A1 WO 2012117089A1
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Prior art keywords
alkyl
compound
cor
formula
membered heteroaryl
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PCT/EP2012/053605
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French (fr)
Inventor
Helmut Reichelt
Thomas Gessner
Klaus MÜLLEN
Chen Li
Glauco BATTAGLIARIN
Original Assignee
Basf Se
MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V.
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Application filed by Basf Se, MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. filed Critical Basf Se
Priority to KR1020137025714A priority Critical patent/KR20130128468A/en
Priority to CN201280011521.6A priority patent/CN103492387A/en
Priority to JP2013555885A priority patent/JP2014514256A/en
Priority to EP12707548.9A priority patent/EP2681217A1/en
Publication of WO2012117089A1 publication Critical patent/WO2012117089A1/en

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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
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • 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
    • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
    • C09B5/62—Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K99/00—Subject matter not provided for in other groups of this subclass
    • 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 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.
  • a 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
  • an electronic device including the composition.
  • 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-perylenedicarboxyimide.
  • US 7,326,956 B2 describes a thin film transitor comprising a layer of organic semiconductor material comprising tetracarboxylic diimide 3,4,9,10-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 ⁇ , ⁇ '-diaryl perylene-based tetracarboxylic diimide compound is represented by the following structure: 1
  • 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 sub- stituent groups on the perylene can include a long list of substituents, including halogens such as fluorine or chlorine, and cyano.
  • US 7,671 ,202 B2 describes n-type semiconductor compounds of formula
  • each R 1 to R 8 , R 11 and R 12 can be independently selected from H, an electron- withdrawing substituent and a moiety comprising such substituent. Electron-withdrawing substi- tutents include a long list of substituents, including cyano.
  • R 9 and R 10 are independently selected from H, alkyi, substituted alkyi, cycloalkyi, substituted cycloalkyi, aryl, substituted aryl, polycyclic aryl and/or substituted polycyclic aryl moieties. At least one of R 1 , R 4 , R 5 , R 8 , R 11 and R 12 can be a cyano substituent.
  • Such cyanated compounds can be di- or tetra-substituted as shown by the following structures:
  • 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 diimide-based semiconductor compounds.
  • the compound can have formula
  • R 1 at each occurrence is independently selected from a long list of groups, including branched C 3 -2o-alkyl and branched C 3 -2o-alkenyl.
  • 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.
  • at least one of R 3 , R 4 , R 5 and R 6 can be Br or cyano.
  • the semiconducting compound can include
  • WO 2009/144205 describes bispolycyclic rylene-based semiconducting materials, for example
  • the object is solved by the compound of claim 1 , the process of claim 2, the compound of claim 6, and the electronic device of claim 7.
  • the perylene-based semiconducting compound of the present invention is of formula 1
  • R 1 and R 2 are independently selected from the group consisting of H, Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl, wherein if R 1 or R 2 are Ci-30-alkyl, C 2 -3o-alkenyl or C 2 -3o-alkynyl, this R 1 or R 2 can be optionally substituted with 1 to 6 groups independently selected from the group consisting of halogen, -CN , -NO2, -OH , Ci-10-alkoxy, -O-CH 2 CH 2 O-Ci-i 0 -alkyl, -O-COR 3 , -S-Ci-io-alkyl, -N H 2 , -N H R 3 ,
  • R 1 or R 2 are C3-io-cycloalkyl, Cs-io-cycloalkenyl or 3-14 membered cycloheteroalkyl, this R 1 or R 2 can be optionally substituted with 1 to 6 groups independently selected from the group consisting of halogen, -CN , -NO2, -OH , Ci-io-alkoxy, -O-CH 2 CH 2 O-Ci-i 0 -alkyl, -O-COR 3 , -S-Ci-io
  • 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, ferf-butyl, n-pentyl, neopentyl, isopentyl, n-(1 -ethyl)propyl, n-hexyl, n-heptyl, n-octyl, n-(2-ethyl)hexyl, n-nonyl and n-decyl.
  • C3-8-alkyl examples include n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, ferf-butyl, n-pentyl, neopentyl, isopentyl, n-(1 -ethyl)propyl, n-hexyl, n-heptyl, n-octyl and n-(2-ethyl)hexyl.
  • Ci-3o-alkyl examples are Ci-10-alkyl, and n-undecyl, n-dodecyl, n-undecyl, n-dodecyl, n-tridecyl,
  • n-tetradecyl n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-icosyl (C20), n-docosyl (C 22 ), n-tetracosyl (C 24 ), n-hexacosyl (03 ⁇ 4), n-octacosyl (C 2 e) and n-triacontyl
  • C 2 -io-alkenyl and C 2 -3o-alkenyl can be branched or unbranched.
  • Examples of C 2 -io-alkenyl are vinyl, propenyl, c/s-2-butenyl, frans-2-butenyl, 3-butenyl, c/s-2-pentenyl, frans-2-pentenyl, c/s-3-pentenyl, frans-3-pentenyl, 4-pentenyl, 2-methyl-3-butenyl, hexenyl, heptenyl, octenyl, nonenyl and docenyl.
  • C2-3o-alkenyl examples include C2-io-alkenyl, and linoleyl (Cie), linolenyl (Cie), oleyl (Cie), arachidonyl (C20), and erucyl (C22).
  • C2-io-alkynyl and C2-3o-alkynyl can be branched or unbranched.
  • Examples of C2-io-alkynyl are ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl and de- cynyl.
  • C2-3o-alkynyl examples include C2-io-alkynyl, and undecynyl, dodecynyl, undecynyl, dode- cynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonade- cynyl and icosynyl (C20).
  • C3-io-cycloalkyl are preferably monocyclic C3-io-cycloalkyls such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, but include also polycyclic C3-io-cycloalkyls such as decalinyl, norbornyl and adamantyl.
  • Cs-io-cycloalkenyl are preferably monocyclic Cs-io-cycloalkenyls such as cyclopen- tenyl, cyclohexenyl, cyclohexadienyl and cycloheptatrienyl, but include also polycyclic
  • 3-14 membered cycloheteroalkyi are monocyclic 3-8 membered cycloheteroalkyi and polycyclic, for example bicyclic 7-12 membered cycloheteroalkyi.
  • monocyclic 3-8 membered cycloheteroalkyi examples include 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
  • 6 membered cycloheteroalkyi containing one heteroatom such as piperidyl, piperidino, tetrahy- dropyranyl, pyranyl, thianyl and thiopyranyl
  • monocyclic 6 membered cycloheteroalkyi contain- ing two heteroatoms such as piperazinyl, morpholinyl and morpholino and thiazinyl, monocyclic
  • 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.
  • 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 het- eroatoms such as tetrazolyl, monocyclic 6 membered heteroaryl containing
  • 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 heteroa- toms 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
  • 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-10-alkoxy examples are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, ferf-butoxy, n-pentoxy, neopentoxy, isopentoxy, hexoxy, n-heptoxy, n-octoxy, n-nonoxy and n-decoxy.
  • Examples of C2-5-alkylene are ethylene, propylene, butylene and pentylene.
  • R 1 and R 2 are independently selected from the group consisting of H , Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, 3-14 membered cyclohetero- alkyl, wherein if R 1 or R 2 are Ci-30-alkyl, C2-3o-alkenyl or C2-3o-alkynyl, this R 1 or R 2 can be optionally substituted with 1 to 6 groups independently selected from the group consisting of halogen, -CN , -NO2, -OH , Ci-10-alkoxy, -O-CH 2 CH 2 O-Ci-i 0 -alkyl, -O-COR 3 , -S-Ci-10-alkyl, -N H 2 , -N H R 3 , -N R3R 4 , -N H-COR 3 ,
  • R 1 or R 2 are C3-io-cycloalkyl, Cs-io-cycloalkenyl or 3-14 membered cycloheteroalkyl, this R 1 or R 2 can be optionally substituted with 1 to 6 groups independently selected from the group consisting of halogen, -CN , -NO2, -OH , Ci-10-alkoxy, -O-CH 2 CH 2 O-Ci-i 0 -alkyl, -O-COR 3 ,
  • R 1 and R 2 are independently selected from the group consisting of H ,
  • R 1 and R 2 are independently from each other Ci-30-alkyl, wherein R 1 or R 2 can be optionally substituted with 1 to 6 groups independently selected from the group consisting of halogen, -CN , -NO2, -OH , Ci-10-alkoxy, -0-CH2CH 2 0-Ci-io-alkyl, -0-COR 3 , -S-Ci-io-alkyl, -N H 2 , -N H R 3 , -N R 3 R 4 , -N H-COR 3 , -COOH , -COOR 3 , -CON H2, -CON H R 3 , -CON R 3 R 4 , -CO-H , -COR 3 , C 3 -i 0 -cycloalkyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl; wherein R 3 and R 4 are at each other Ci-30-
  • R 1 and R 2 are the same and are Ci- 3 o-alkyl, preferably C 3 -8-alkyl, wherein R 1 or R 2 can be optionally substituted with 1 to 6 groups independently selected from the group consisting of halogen, -CN , -NO2, -OH , Ci-10-alkoxy, -0-CH 2 CH 2 0-Ci-io-alkyl, -0-COR 3 , -S-Ci-io-alkyl, -N H 2 , -N H R 3 , -N R 3 R 4 , -N H-COR 3 , -COOH , -COOR 3 , -CON H2, -CON H R 3 , -CON R 3 R 4 , -CO-H , -COR 3 , C 3 -i 0 -cycloalkyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered hetero
  • R 1 and R 2 are the same and are unsubstituted Ci- 3 o-alkyl, preferably unsubstituted C 3 -8-alkyl such as n-(1 -ethyl)propyl. Also part of the invention, is a process for the preparation of the compound of formula 1
  • 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-ferf-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 tempera- tures, such as at temperatures from 60 to 1 10 °C.
  • 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. Hart- wig in Chem. Rev. 2010, 110, 890-931 .
  • the first step is usually 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 cyanide source in step two can be tetra-Ci-io-alkylammoniumcyanide, tetra-Ci-io-alkylphosphoniumcyanide or hexa-Ci-io-alkylguanidiniumcyanide.
  • the cyanide source in step two can be Zn(CN) 2 .
  • the second step is usually performed in the presence of a base such as CsF and a copper reagent such as Cu(N0 3 )2.
  • the second step is usually performed in a suitable solvent such as water, methanol and dioxane, or mixtures thereof.
  • the second step is usually performed at elevated temperatures, such as at temperatures from 80 to 120 °C.
  • step two 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 .
  • 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 invention are the compounds of formula
  • R 1 , R 2 and L are as defined above.
  • Also part of the present invention is an electronic device comprising the compound of formula (1 ) as semiconducting material.
  • Also part of the invention is the use of the compound of formula (1 ) as semiconducting material.
  • the compounds of formula (1 ) show a high charge carrier mobility and a high stability, in particular towards oxidation, under ambient conditions. Furthermore the compounds of formula (1 ) are compatible with liquid processing techniques. Examples
  • A/,/V'-Bis(1 -ethylpropyl) perylene-3,4:9,10-tetracarboxylic acid bisimide (2a) (100 mg, 0,189 mmol) and bispinacolondiboronate (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. RuH 2 (CO)(PPh3)3 (0,082 mg, 0,09 mmol) is added to the reaction mixture and the ves- sel 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,
  • the reaction vessel is closed and heated in microwave for 1 hour at 100 °C.
  • the reaction mixture is then poured into a saturated solution of ammonium chloride and extracted with dichloromethane.
  • the organic phase is dried over magnesium sulfate and the solvent evaporated.
  • the product is purified via column chromatography (silica, dichloromethane/acetone 50/1 ) and obtained as a red-orange solid (yield 40%, 13 mg, 0,019 mmol).
  • A/,/V'-Bis(1 -heptyloctyl) perylene-3,4:9,10-tetracarboxylic acid bisimide (2b) (0,12 mmol) and bispinacolondiboronate (3a) (0.99mmol) are mixed together and dissolved in 2 ml. dry mesity- lene and 0,15 ml. dry pinacolone. Argon is bubbled trough the solution for 30 minutes.
  • RuH 2 (CO)(PPh 3 )3 (0.06 mmol) is added to the reaction mixture and the vessel heated to 140°C for 24 hours. After cooling the system to room temperature, the solvent is evaporated and the desired compound 4b is purified by column chromatography (silica, Ch C /AcOEt 50/1 ).
  • HMDS hexamethyldisilazane
  • Source/drain electrodes (Ta (thickness: 10 nm) covered by Au (thick- ness: 40 nm)) are deposited on the HM PS-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 5 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 2.
  • FIG 3 the charge carrier mobility [cm s] in relation to the gate voltage VSG [V] for the bottom-gate organic field effect transistor of example 5 comprising compound 1 b as semiconducting material is shown.
  • the average values and the 90% confidence interval (in parentheses) of the charge carrier mobility [cmWs], the ION/IOFF ratio and the switch-on voltage Vso [V] for the bottom-gate organic field effect transistor of example 5 comprising compound 1 b as semiconducting material is 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).

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  • Organic Chemistry (AREA)
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Abstract

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

Description

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.
The use of perylene-based organic semiconducting materials in electronic devices is known in the art.
US 7,282,275 B2 describes a composition that includes
a first compound of formula [EC-]n-Ar1 (I), wherein
A1 is a first aromatic core and is a divalent, trivalent or tetravalent radical of a long list of formulae, including
Figure imgf000002_0001
that is unsubstituted or substituted with a long list of substituents, including fluoro and cyano,
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 processible.
Also provided is an electronic device including the composition.
US 7,355,198 B2 describes am 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-perylenedicarboxyimide.
US 7,326,956 B2 describes a thin film transitor comprising a layer of organic semiconductor material comprising tetracarboxylic diimide 3,4,9,10-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 Ν,Ν'-diaryl perylene-based tetracarboxylic diimide compound is represented by the following structure: 1
Figure imgf000003_0001
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 sub- stituent groups on the perylene can include a long list of substituents, including halogens such as fluorine or chlorine, and cyano. US 7,671 ,202 B2 describes n-type semiconductor compounds of formula
Figure imgf000004_0001
wherein each R1 to R8, R11 and R12 can be independently selected from H, an electron- withdrawing substituent and a moiety comprising such substituent. Electron-withdrawing substi- tutents include a long list of substituents, including cyano. R9 and R10 are independently selected from H, alkyi, substituted alkyi, cycloalkyi, substituted cycloalkyi, aryl, substituted aryl, polycyclic aryl and/or substituted polycyclic aryl moieties. At least one of R1, R4, R5, R8, R11 and R12 can be a cyano substituent. Such cyanated compounds can be di- or tetra-substituted as shown by the following structures:
Figure imgf000004_0002
WO 2005/124453 describes perylenetetracarboxylic diimide charge-transfer materials, for example a perylenetetracarboxylic diimide charge-transfer material having formula
Figure imgf000005_0001
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 diimide-based semiconductor compounds. In a particular embodi- ment the compound can have formula
Figure imgf000005_0002
wherein R1 at each occurrence is independently selected from a long list of groups, including branched C3-2o-alkyl and branched C3-2o-alkenyl.
WO 2009/098252 describes semiconducting compounds having formula
Figure imgf000006_0001
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, at least one of R3, R4, R5 and R6 can be Br or cyano. For example, the semiconducting compound can include
Figure imgf000006_0002
WO 2009/144205 describes bispolycyclic rylene-based semiconducting materials, for example
Figure imgf000006_0003
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 tetracaroxylic acid bisim- ides from perylene tetracarboxylic acid bisimides
Figure imgf000007_0001
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 2, the compound of claim 6, and the electronic device of claim 7.
The perylene-based semiconducting compound of the present invention is of formula 1
Figure imgf000007_0002
wherein
R1 and R2 are independently selected from the group consisting of H, Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl, wherein if R1 or R2 are Ci-30-alkyl, C2-3o-alkenyl or C2-3o-alkynyl, this R1 or R2 can be optionally substituted with 1 to 6 groups independently selected from the group consisting of halogen, -CN , -NO2, -OH , Ci-10-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR3, -S-Ci-io-alkyl, -N H2, -N H R3,
-N R3R4, -N H-COR3, -COOH , -COOR3, -CON H2, -CO N H R3, -CON R3R4, -CO-H , -COR3, C3-io-cycloalkyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl; if R1 or R2 are C3-io-cycloalkyl, Cs-io-cycloalkenyl or 3-14 membered cycloheteroalkyl, this R1 or R2 can be optionally substituted with 1 to 6 groups independently selected from the group consisting of halogen, -CN , -NO2, -OH , Ci-io-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR3, -S-Ci-io-alkyl, -N H2, -N H R3, -N R3R4, -N H-COR3, -COOH , -COOR3, -CON H2, -CO N H R3, -CON R3R4, -CO-H , -COR3, Ci-io-alkyl, C2-io-alkenyl, C2-io-alkynyl, C6-i4-aryl and 5-14 membered heteroaryl; if R1 or R2 are C6-i4-aryl or 5-14 membered heteroaryl, this R1 or R2 can be optionally substituted with 1 to 6 groups independently selected from the group consisting of halogen, -CN , -NO2, -OH , Ci-io-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR3, -S-Ci-io-alkyl, -N H2, -N H R3, -N R3R4, -N H-COR3, -COOH , -COOR3, -CON H2, -CO N H R3, -CON R3R4, -CO-H , -COR3, Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl and 3-14 membered cycloheteroalkyl, wherein R3 and R4 are at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, 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, ferf-butyl, n-pentyl, neopentyl, isopentyl, n-(1 -ethyl)propyl, n-hexyl, n-heptyl, n-octyl, n-(2-ethyl)hexyl, n-nonyl and n-decyl. Examples of C3-8-alkyl are n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, ferf-butyl, n-pentyl, neopentyl, isopentyl, n-(1 -ethyl)propyl, n-hexyl, n-heptyl, n-octyl and n-(2-ethyl)hexyl. Examples of Ci-3o-alkyl are Ci-10-alkyl, and n-undecyl, n-dodecyl, 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 (0¾), n-octacosyl (C2e) and n-triacontyl
C2-io-alkenyl and C2-3o-alkenyl can be branched or unbranched. Examples of C2-io-alkenyl are vinyl, propenyl, c/s-2-butenyl, frans-2-butenyl, 3-butenyl, c/s-2-pentenyl, frans-2-pentenyl, c/s-3-pentenyl, frans-3-pentenyl, 4-pentenyl, 2-methyl-3-butenyl, hexenyl, heptenyl, octenyl, nonenyl and docenyl. Examples of C2-3o-alkenyl are C2-io-alkenyl, and linoleyl (Cie), linolenyl (Cie), oleyl (Cie), arachidonyl (C20), and erucyl (C22).
C2-io-alkynyl and C2-3o-alkynyl can be branched or unbranched. Examples of C2-io-alkynyl are ethynyl, 2-propynyl, 2-butynyl, 3-butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl and de- cynyl. Examples of C2-3o-alkynyl are C2-io-alkynyl, and undecynyl, dodecynyl, undecynyl, dode- cynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonade- cynyl and icosynyl (C20). Examples of C3-io-cycloalkyl are preferably monocyclic C3-io-cycloalkyls such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, but include also polycyclic C3-io-cycloalkyls such as decalinyl, norbornyl and adamantyl.
Examples of Cs-io-cycloalkenyl are preferably monocyclic Cs-io-cycloalkenyls such as cyclopen- tenyl, cyclohexenyl, cyclohexadienyl and cycloheptatrienyl, but include also polycyclic
Cs-io-cycloalkenyls.
Examples of 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 contain- ing 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 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 het- eroatoms such as tetrazolyl, monocyclic 6 membered heteroaryl containing one heteroatom such as pyridyl, monocyclic 6 membered heteroaryl containing two heteroatoms such as pyraz- inyl, 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 heteroa- toms 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-10-alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, ferf-butoxy, n-pentoxy, neopentoxy, isopentoxy, hexoxy, n-heptoxy, n-octoxy, n-nonoxy and n-decoxy. Examples of C2-5-alkylene are ethylene, propylene, butylene and pentylene. Preferably, R1 and R2 are independently selected from the group consisting of H , Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, 3-14 membered cyclohetero- alkyl, wherein if R1 or R2 are Ci-30-alkyl, C2-3o-alkenyl or C2-3o-alkynyl, this R1 or R2 can be optionally substituted with 1 to 6 groups independently selected from the group consisting of halogen, -CN , -NO2, -OH , Ci-10-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR3, -S-Ci-10-alkyl, -N H2, -N H R3, -N R3R4, -N H-COR3, -COOH , -COOR3, -CON H2, -CO N H R3, -CON R3R4, -CO-H , -COR3,
C3-io-cycloalkyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl; if R1 or R2 are C3-io-cycloalkyl, Cs-io-cycloalkenyl or 3-14 membered cycloheteroalkyl, this R1 or R2 can be optionally substituted with 1 to 6 groups independently selected from the group consisting of halogen, -CN , -NO2, -OH , Ci-10-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR3,
-S-Ci-10-alkyl, -N H2, -N H R3, -N R3R4, -N H-COR3, -COOH , -COOR3, -CON H2, -CO N H R3, -CON R3R4, -CO-H , -COR3, Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C6-i4-aryl and 5-14 membered heteroaryl; wherein R3 and R4 are at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl.
More preferably, R1 and R2 are independently selected from the group consisting of H ,
Ci-3o-alkyl, C2-3o-alkenyl, wherein if R1 or R2 are Ci-30-alkyl or C2-3o-alkenyl, this R1 or R2 can be optionally substituted with 1 to 6 groups independently selected from the group consisting of halogen, -CN , -NO2, -OH , Ci-10-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR3, -S-Ci-10-alkyl, -N H2, -N H R3, -N R3R4, -N H-COR3, -COOH , -COOR3, -CON H2, -CO N H R3, -CON R3R4, -CO-H , -COR3, C3-io-cyclo- alkyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl; wherein R3 and R4 are at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl. Even more preferably, R1 and R2 are independently from each other Ci-30-alkyl, wherein R1 or R2 can be optionally substituted with 1 to 6 groups independently selected from the group consisting of halogen, -CN , -NO2, -OH , Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -0-COR3, -S-Ci-io-alkyl, -N H2, -N H R3, -N R3R4, -N H-COR3, -COOH , -COOR3, -CON H2, -CON H R3, -CON R3R4, -CO-H , -COR3, C3-i0-cycloalkyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl; wherein R3 and R4 are at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, C5-io-cycloalkenyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl.
Most preferably, R1 and R2 are the same and are Ci-3o-alkyl, preferably C3-8-alkyl, wherein R1 or R2 can be optionally substituted with 1 to 6 groups independently selected from the group consisting of halogen, -CN , -NO2, -OH , Ci-10-alkoxy, -0-CH2CH20-Ci-io-alkyl, -0-COR3, -S-Ci-io-alkyl, -N H2, -N H R3, -N R3R4, -N H-COR3, -COOH , -COOR3, -CON H2, -CON H R3, -CON R3R4, -CO-H , -COR3, C3-i0-cycloalkyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl; wherein R3 and R4 are at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, C5-io-cycloalkenyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl.
In particular, R1 and R2 are the same and are unsubstituted Ci-3o-alkyl, preferably unsubstituted C3-8-alkyl such as n-(1 -ethyl)propyl. Also part of the invention, is a process for the preparation of the compound of formula 1
Figure imgf000013_0001
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)
Figure imgf000013_0002
(2) (3) (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 cyanide 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-ferf-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 tempera- tures, 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. Hart- wig in Chem. Rev. 2010, 110, 890-931 .
If the transition metal-containing catalyst is a ruthenium-containing catalyst, the first step is usually 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.
In one embodiment, the cyanide source in step two can be tetra-Ci-io-alkylammoniumcyanide, tetra-Ci-io-alkylphosphoniumcyanide or hexa-Ci-io-alkylguanidiniumcyanide.
In a second embodiment, the cyanide source in step two can be Zn(CN)2.
The second step is usually performed in the presence of a base such as CsF and a copper reagent such as Cu(N03)2. The second step is usually performed in a suitable solvent such as water, methanol and dioxane, or mixtures thereof. The second step is usually performed at elevated temperatures, such as at temperatures from 80 to 120 °C.
In principal, if the metal cyanide is Zn(CN)2, step two 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 .
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 invention are the compounds of formula
Figure imgf000015_0001
wherein R1, R2 and L are as defined above.
Also part of the present invention is an electronic device comprising the compound of formula (1 ) as semiconducting material.
Also part of the invention is the use of the compound of formula (1 ) as semiconducting material.
In Figure 1 the design of the bottom-gate organic field effect transistor of example 5 is shown.
In Figure 2 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 5 comprising compound 1 b as semiconducting material at a drain voltage VSD of 1 00 V is shown.
In Figure 3 the charge carrier mobility [cmWs] in relation to the gate voltage VSG [V] for the bottom-gate organic field effect transistor of example 5 comprising compound 1 b as semiconducting material is shown.
The compounds of formula (1 ) show a high charge carrier mobility and a high stability, in particular towards oxidation, under ambient conditions. Furthermore the compounds of formula (1 ) are compatible with liquid processing techniques. Examples
Example 1
Preparation of A/,/V'-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)
Figure imgf000016_0001
A/,/V'-Bis(1 -ethylpropyl) perylene-3,4:9,10-tetracarboxylic acid bisimide (2a) (100 mg, 0,189 mmol) and bispinacolondiboronate (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 ves- sel 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).
1H NMR (250 MHz, CD2CI2) δ 8.59 (s, J = 7.3 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 Spectrum (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 1cm 1. Fluorescence Quantum Yield: 0,89. Elemental Analysis: theoreticahC, 67.34; H, 7.21 ; N , 2.71 ;experimental: C, 67.29; H, 7.40; N, 2.96. Example 2
Preparation of A/,/V'-bis(1 -ethylpropyl)-2,5,8,1 1 -tetracarbonitrile-perylene-3,4:9,10-tetra- carboxylic acid bisimide (1a)
Figure imgf000017_0001
(1a) , '-Bis(1 -ethylpropyl)-2,5,8,1 1 -tetrakis[4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-y]pei len 3,4:9,10-tetracarboxylic acid bisimide (4a) (50 mg, 0,048 mmol), zinc cyanide (68 mg,0,58 mmol) caesium fluoride (29 mg, 0,19 mmol) and copper nitrate (90 mg, 0,38) are suspended in a mixture of water (1 ml_), methanol (1 ml.) and dioxane (1 ml_). The reaction vessel is closed and heated in microwave for 1 hour at 100 °C. The reaction mixture is then poured into a saturated solution of ammonium chloride and extracted with dichloromethane. The organic phase is dried over magnesium sulfate and the solvent evaporated. The product is purified via column chromatography (silica, dichloromethane/acetone 50/1 ) and obtained as a red-orange solid (yield 40%, 13 mg, 0,019 mmol).
1H NMR (250 MHz, CD2CI2) δ 8.98 (s, 4H), 5.09 (m, 2H), 2.38 - 2.16 (m, 4H), 2.1 1 - 1.90 (m, 4H), 0.96 (t, J = 7.5 Hz, 12H). FD Mass Spectrum (8kV): m/z= 630,9 (100%) [M+]. Absorption: 517 nm (in CH2CI2). Emission: 525 nm (in CH2CI2, exc 517 nm). Extinction Coefficient: 7,31 x 104 M-1cm-1. Example 3
Preparation of A/,/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 (4b)
Figure imgf000018_0001
A/,/V'-Bis(1 -heptyloctyl) perylene-3,4:9,10-tetracarboxylic acid bisimide (2b) (0,12 mmol) and bispinacolondiboronate (3a) (0.99mmol) are mixed together and dissolved in 2 ml. dry mesity- lene and 0,15 ml. dry pinacolone. Argon is bubbled trough the solution for 30 minutes.
RuH2(CO)(PPh3)3 (0.06 mmol) is added to the reaction mixture and the vessel heated to 140°C for 24 hours. After cooling the system to room temperature, the solvent is evaporated and the desired compound 4b is purified by column chromatography (silica, Ch C /AcOEt 50/1 ).
Example 4
Preparation of A/,/V'-bis(1 -heptyloctyl)-2,5,8,1 1 -tetracyano-perylene-3,4:9,10-tetracarboxylic acid bisimide (1 b)
Figure imgf000019_0001
(1 b) ^'-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) (63 mg, 0.05 mmol), prepared as described in exam- pie 3, cesium fluoride (29 mg, 0.19 mmol), zinc cyanide (68 mg, 0.58 mmol) and copper(ll) nitrate x 2.5 H2O (89 mg, 0.38 mmol) are suspended in 3 mL of a 5/1 mixture of dioxane/methanol and heated in a microwave vessel at 80 °C for 5 minutes. The reaction mixture is then poured in a saturated solution of ammonium chloride and extracted with dichloromethane. The organic phase is dried over magnesium sulfate and the solvent evaporated. The desired compound is obtained as a brownish solid after column chromatography (silica, dichloromethane) in 40% yield (18 mg, 0.019 mmol). 1 H NMR (500 MHz, CD2CI2) δ 8.99 (s, 4H), 5.25-5.14 (m, 2H), 2.30- 2.12 (m, 4H), 1.93 (m, 4H), 1.29 (m, 40H), 0.84 (t, J = 5.7 Hz, 12H). 13C NMR (126 MHz, CD2CI2) δ 161 .33 (s), 133.20 (s), 131 .01 (s), 129.89 (s), 128.74 (s), 127.35 (s), 1 17.63 (s), 1 17.26 (s), 57.17 (s), 32.61 (s), 32.32 (s), 29.97 (s), 29.74 (s), 27.51 (s), 23.16 (s), 14.38 (s). FD/MS (8kV): m/z = 909.9 (100%) [M+]. UV-Vis (in dichloromethane, ma* (ε [M 1 cm 1]: 518 nm (7.0 x 104 M 1 cm 1). Fluorescence (in dichloromethane, λβχ = 528 nm. φβχ: 0.55. Elem. Anal.: theoretical: C: 76.46%, H: 7.30%; N: 9.22%; experimental: C: 76.80%; H: 6.98%; N : 9.50%. Example 5
Preparation of bottom-gate organic field effect transistors containing compound 1 b 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 HM PS-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 HM PS-treated side of the dielectric layer by vapour deposition. The channel length is 20 μιη 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 in chloroform (concentration = 10 mg/mL) in a nitrogen filled glove box (O2 content: 0.1 ppm, H20 content: 0.0 ppm, pressure: 1 120 Pa, tempera- ture: 17 °C) using a Keithley 4200 machine.
The design of the bottom-gate organic field effect transistor of example 5 is shown in Figure 1 .
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 5 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 2.
In Figure 3 the charge carrier mobility [cm s] in relation to the gate voltage VSG [V] for the bottom-gate organic field effect transistor of example 5 comprising compound 1 b as semiconducting material is shown. The average values and the 90% confidence interval (in parentheses) of the charge carrier mobility [cmWs], the ION/IOFF ratio and the switch-on voltage Vso [V] for the bottom-gate organic field effect transistor of example 5 comprising compound 1 b as semiconducting material is 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).
Figure imgf000020_0001
Table 1 .

Claims

Claims
Figure imgf000021_0001
wherein
R1 and R2are independently selected from the group consisting of H, Ci-30-alkyl, C2-3o-alkenyl, C2-3o-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl, wherein if R1 or R2 are Ci-30-alkyl, C2-3o-alkenyl or C2-3o-alkynyl, this R1 or R2 can be optionally substituted with 1 to 6 groups independently selected from the group consisting of halogen, -CN, -NO2, -OH, Ci-10-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR3, -S-Ci-io-alkyl, -NH2, -NHR3, -NR3R4, -NH-COR3, -COOH, -COOR3, -CONH2, -CO NHR3, -CONR3R4, -CO-H, -COR3, C3-io-cycloalkyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl; if R1 or R2 are C3-io-cycloalkyl, Cs-io-cycloalkenyl or 3-14 membered cycloheteroalkyl, this R1 or R2 can be optionally substituted with 1 to 6 groups independently selected from the group consisting of halogen, -CN, -NO2, -OH, Ci-io-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR3, -S-Ci-io-alkyl, -NH2, -NHR3, -NR3R4, -NH-COR3, -COOH, -COOR3, -CONH2, -CO NHR3,
-CONR3R4, -CO-H, -COR3, Ci-io-alkyl, C2-io-alkenyl, C2-io-alkynyl, C6-i4-aryl and 5-14 membered heteroaryl; if R1 or R2 are C6-i4-aryl or 5-14 membered heteroaryl, this R1 or R2 can be optionally substi- tuted with 1 to 6 groups independently selected from the group consisting of halogen, -CN, -NO2, -OH, Ci-io-alkoxy, -O-CH2CH2O-Ci-i0-alkyl, -O-COR3, -S-Ci-io-alkyl, -NH2, -NHR3, -NR3R4, -NH-COR3, -COOH, -COOR3, -CONH2, -CO NHR3, -CONR3R4, -CO-H, -COR3, Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, Cs-io-cycloalkenyl and 3-14 membered cycloheteroalkyl, wherein R3 and R4 are at each occurrence are independently from each other selected from the group consisting of Ci-10-alkyl, C2-io-alkenyl, C2-io-alkynyl, C3-io-cycloalkyl, C5-io-cycloalkenyl, 3-14 membered cycloheteroalkyl, C6-i4-aryl and 5-14 membered heteroaryl.
2. A process for the preparation of the compound of formula (1 ) of 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)
Figure imgf000022_0001
(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 cyanide source in order to form the compound of formula (1 ).
3. The process of claim 2, wherein in the compound of formula (4) L is C2-5-alkylene, which can be optionally substituted with 1 to 6 Ci-10-alkyl groups.
4. The process of claim 2 or claim 3, wherein the cyanide source in step (ii) is selected from the group consisting of tetra-Ci-io-alkylammoniumcyanide, tetra-Ci-io-alkylphosphoniumcyanide and hexa-Ci-io-alkylguanidiniumcyanide.
5. The process of claim 2 or claim 3, wherein the cyanide source in step (ii) is Zn(CN)2.
6. A compound of formula
Figure imgf000023_0001
(4) wherein R1, R2 are as defined in claim 1 and L is as defined in claim 2 or claim 3.
7. An electronic device comprising the compound of formula (1 ) of claim 1 as semiconducting material.
8. Use of the compound of formula (1 ) of claim 1 as semiconducting material.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104045657A (en) * 2013-03-14 2014-09-17 中国科学院化学研究所 Five-membered heterocyclic derivative-bridged perylene diimide dipolymer and its preparation method and use in organic photovoltaic device
US9583719B2 (en) 2011-08-12 2017-02-28 Basf Se Carbazolocarbazol-bis(dicarboximides) and their use as semiconductors
WO2019170481A1 (en) 2018-03-07 2019-09-12 Basf Se Patterning method for preparing top-gate, bottom-contact organic field effect transistors
WO2019170719A1 (en) 2018-03-08 2019-09-12 Basf Se Organic field effect transistor comprising semiconducting single-walled carbon nanotubes and organic semiconducting material
WO2020001865A1 (en) 2018-06-26 2020-01-02 Basf Se Vinylether-based polymer as dielectric

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050176970A1 (en) * 2004-01-26 2005-08-11 Marks Tobin J. Perylene n-type semiconductors and related devices
WO2005124453A2 (en) 2004-06-14 2005-12-29 Georgia Tech Research Corporation Perylene charge-transport materials, methods of fabrication thereof, and methods of use thereof
US7282275B2 (en) 2002-04-19 2007-10-16 3M Innovative Properties Company Materials for organic electronic devices
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
US7355198B2 (en) 2004-04-29 2008-04-08 Samsung Sdi Co., Ltd. Organic thin film transistor including organic acceptor film
WO2008063609A2 (en) 2006-11-17 2008-05-29 Polyera Corporation Diimide-based semiconductor materials and methods of preparing and using the same
WO2008085942A2 (en) * 2007-01-08 2008-07-17 Polyera Corporation Methods for preparing arene-bis(dicarboximide)-based semiconducting materials and related intermediates for preparing same
WO2009098252A1 (en) 2008-02-05 2009-08-13 Basf Se Perylene semiconductors and methods of preparation and use thereof
WO2009144205A1 (en) 2008-05-30 2009-12-03 Basf Se Rylene-based semiconductor materials and methods of preparation and use thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3542485A1 (en) * 1985-11-30 1987-06-04 Bayer Ag Radical-ion salts of derivatives of 1,4,5,8-naphthalenetetracarboxylic acid, and process for preparing them
JP5627459B2 (en) * 2007-08-17 2014-11-19 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Halogen-containing perylenetetracarboxylic acid derivatives and their use
EP2280971A1 (en) * 2008-03-19 2011-02-09 Basf Se N,n'-bis(fluorophenylalkyl)-substituted perylene-3,4:9,10-tetracarboximides, and the preparation and use thereof
US8471020B2 (en) * 2011-03-03 2013-06-25 Basf Se Perylene-based semiconducting materials
CN103265555B (en) * 2012-05-25 2016-04-13 中国科学院化学研究所 Si Suo Suan perylene diimides compound and preparation method thereof and application

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7282275B2 (en) 2002-04-19 2007-10-16 3M Innovative Properties Company Materials for organic electronic devices
US20050176970A1 (en) * 2004-01-26 2005-08-11 Marks Tobin J. Perylene n-type semiconductors and related devices
US7671202B2 (en) 2004-01-26 2010-03-02 Northwestern University Perylene n-type semiconductors and related devices
US7355198B2 (en) 2004-04-29 2008-04-08 Samsung Sdi Co., Ltd. Organic thin film transistor including organic acceptor film
WO2005124453A2 (en) 2004-06-14 2005-12-29 Georgia Tech Research Corporation Perylene charge-transport materials, methods of fabrication thereof, and methods of use thereof
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
WO2008063609A2 (en) 2006-11-17 2008-05-29 Polyera Corporation Diimide-based semiconductor materials and methods of preparing and using the same
WO2008085942A2 (en) * 2007-01-08 2008-07-17 Polyera Corporation Methods for preparing arene-bis(dicarboximide)-based semiconducting materials and related intermediates for preparing same
WO2009098252A1 (en) 2008-02-05 2009-08-13 Basf Se Perylene semiconductors and methods of preparation and use thereof
WO2009144205A1 (en) 2008-05-30 2009-12-03 Basf Se Rylene-based semiconductor materials and methods of preparation and use thereof

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
C. W. LISKEY; X. LIAO; J. F. HARTWIG, J. AM. CHEM. SOC., vol. 132, 2010, pages 11389 - 11391
CARL W. LISKEY, XUEBIN LIAO, JOHN F. HARTWIG: "Cyanation of arenes via iridium-catalyzed borylation", J. AM. CHEM. SOC., vol. 132, 2 August 2010 (2010-08-02), pages 11389 - 11391, XP002640884 *
F. WURTHNER: "Synthesis", CHEM. COMMUN., 2004, pages 1564 - 1579
I. A. I. MKHALID; J. H. BARNARD; T. B. MARDER; J. M. MURPHY; J. F. HARTWIG, CHEM. REV., vol. 110, 2010, pages 890 - 931
IBRAHEEM A. I. MKHALID, JONATHAN H. BARNARD, TODD B. MARDEWR, JACLYN M. MURPHY, JOHN F. HARTWIG: "C-H activation for the construction of C-B bonds", CHEM. REV., vol. 110, 22 December 2009 (2009-12-22), pages 890 - 931, XP002640883 *
S. NAKANZONO; S. EASWARAMOORTHI; D. KIM; H. SHINOKUBO; A. OSUKA, ORG. LETT., vol. 11, 2009, pages 5426 - 5429
SOICHIRO KAWAMORITA, HIROHISA OHMIYA, KENJI HARA, ATSUSHI FUKUOKA, MASAYA SAWAMURA: "Directed ortho borylation of functionalized arenes catalyzed by a silica-supported compact phosphine-iridium system", J. AM. CHEM. SOC., vol. 131, 24 March 2009 (2009-03-24), pages 5058 - 5059, XP002640882 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9583719B2 (en) 2011-08-12 2017-02-28 Basf Se Carbazolocarbazol-bis(dicarboximides) and their use as semiconductors
CN104045657A (en) * 2013-03-14 2014-09-17 中国科学院化学研究所 Five-membered heterocyclic derivative-bridged perylene diimide dipolymer and its preparation method and use in organic photovoltaic device
WO2019170481A1 (en) 2018-03-07 2019-09-12 Basf Se Patterning method for preparing top-gate, bottom-contact organic field effect transistors
US11296290B2 (en) 2018-03-07 2022-04-05 Clap Co., Ltd. Patterning method for preparing top-gate, bottom-contact organic field effect transistors
US11690236B2 (en) 2018-03-07 2023-06-27 Clap Co., Ltd. Patterning method for preparing top-gate, bottom-contact organic field effect transistors
WO2019170719A1 (en) 2018-03-08 2019-09-12 Basf Se Organic field effect transistor comprising semiconducting single-walled carbon nanotubes and organic semiconducting material
WO2020001865A1 (en) 2018-06-26 2020-01-02 Basf Se Vinylether-based polymer as dielectric

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