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WO2008113753A1 - Procédé de production de diimides de l'acide rylène-tétracarboxylique, dont les azotes imidés portent des atomes d'hydrogène, et leur utilisation - Google Patents

Procédé de production de diimides de l'acide rylène-tétracarboxylique, dont les azotes imidés portent des atomes d'hydrogène, et leur utilisation Download PDF

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WO2008113753A1
WO2008113753A1 PCT/EP2008/053063 EP2008053063W WO2008113753A1 WO 2008113753 A1 WO2008113753 A1 WO 2008113753A1 EP 2008053063 W EP2008053063 W EP 2008053063W WO 2008113753 A1 WO2008113753 A1 WO 2008113753A1
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phenyl
alkyl
radicals
formula
compounds
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Martin KÖNEMANN
Frank WÜRTHNER
Peter Osswald
Theo Kaiser
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Basf Se
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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
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/731—Liquid crystalline materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • 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
    • H10K85/791—Starburst compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a process for the preparation of rylenetetracarboximides, whose imide nitrogens carry hydrogen atoms, and to their use, in particular as organic semiconductors in excitonic solar cells.
  • R 1 and R 2 are independently hydrogen, substituted or unsubstituted alkyl or substituted or unsubstituted aryl;
  • X and Y independently of one another are hydrogen, halogen, amino or a radical having the formula -NHR 3 , -OR 3 , where R 3 has the formula -CH 2 R 4 , -CHR 4 R 5 , or -CR 4 R 5 R 6 wherein R 4 , R 5 , R 6 are independently hydrogen, substituted or unsubstituted alkyl, aryl, alkoxy, alkylthio, aryloxy, arylthio, wherein at least one of the two substituents X, Y is not hydrogen, halogen.
  • DE 102 33 955 describes a process for the preparation of quaterrylenetetracarboxylic diimides whose imide nitrogens can carry, inter alia, hydrogen atoms in addition to a large number of other radicals.
  • the preparation takes place starting from perylene-3,4: 9,10-tetracarboxylic acid-3,4-anhydride-9,10-imides via a dimerizing decarboxylation and subsequent cyclization.
  • DE 10 2004 003 735 describes a process for the preparation of terrylene-3,4: 11, 12-tetracarboxylic diimides.
  • a diborane reacted with ai) a 9-bromoperylene-3,4-dicarboximide or a2) a naphthalene-1, 8-dicarboximide IHb.
  • the resulting 9- (dioxaborolan-2-yl) -perylene-3,4-dicarboximide or 4- (dioxaborolan-2-yl) naphthalene-1,8-dicarboxylic acid imide is isolated in a second step b) of a Suzuki Coupling reaction with a naphthalene-1, 8-dicarboximide (b1) or a 9-bromoperylene-3,4-dicar-bimide (b2) subjected.
  • step b) The 9- (4-naphthalene-1, 8-dicarboximide) -perylene-3,4-dicarboximide obtained in step b) is finally converted into a terrylene-3,4: 11, 12 by cyclodehydration in a third step c) Tetracarbon Acidiimid converted.
  • WO 2005/070895 describes a process for the preparation of terrylene-3,4: 1 1, 12-tetracarboxylic diimides whose imide nitrogens can carry, inter alia, hydrogen atoms.
  • a perylene-3,4-dicarboxylic acid imide is reacted with a naphthalene-1, 8-dicarboximide.
  • R 1 , R 2 , R 3 and R 4 is a substituent selected from Br, F and CN,
  • Y 1 is O or NR a , where R a is hydrogen or an organyl radical,
  • Y 2 is O or NR b , where R b is hydrogen or an organyl radical, Z 1 and Z 2 independently of one another are O or NR C , where R c is an organyl radical,
  • Z 3 and Z 4 are each independently O or NR d , where R d is an organyl radical,
  • R a with a radical R c also together represent a bridging group having 2 to 5 atoms between the flanking bonds can
  • R b with a radical R d together also represent a bridging group having 2 to 5 atoms between the flanking bonds
  • n 2, 3 or 4
  • R n1 , R n2 , R n3 and R n4 is fluorine
  • R n1 , R n2 , R n3 and R n4 is a substituent which is independently selected from Cl and Br, and the other radicals are hydrogen,
  • Y 1 is O or NR a , where R a is hydrogen or an organyl radical
  • Y 2 is O or NR b
  • R b is hydrogen or an organyl radical
  • Z 1 , Z 2 , Z 3 and Z 4 are O
  • one of the radicals Z 1 and Z 2 may also represent NR C , wherein the radicals R a and R c together represent a bridging group having 2 to 5 atoms between the flanking bonds stand, and
  • one of the radicals Z 3 and Z 4 may also represent NR d , where the radicals R b and R d together represent a bridging group having 2 to 5 atoms between the radicals flanking bonds,
  • semiconductors in particular n-semiconductors, in organic electronics, in particular for organic field-effect transistors, solar cells and organic light-emitting diodes.
  • the object of the present invention is to provide long-wave fluorescence colorants with high fluorescence quantum yield. Such compounds would be of interest, inter alia, as fluorescent materials and exciton transport materials in electroluminescent and photovoltaic applications.
  • the present invention is also specifically based on the object of providing rylene compounds for use in organic photovoltaics, in particular as semiconductors in excitonic solar cells.
  • rylenetetracarboxylic diimides in which both imide nitrogens carry hydrogen atoms are particularly advantageously suitable for this use.
  • Fluorescent rylene dyes usually lose their fluorescence upon aggregation. Therefore, it is surprising, on the one hand, that the compounds found form J aggregates and at the same time show long-wave fluorescence with high fluorescence quantum yield. Furthermore, it is also surprising that the compounds found are capable of forming J-aggregates.
  • a first subject of the invention is therefore the use of homo-aggregates of compounds of general formula I.
  • n 1, 2, 3 or 4
  • R n1 , R n2 , R n3 and R n4 is a radical other than hydrogen selected from aryloxy, arylthio, hetaryloxy or
  • hetarylthio as emitter materials, charge transport materials or exciton transport materials.
  • Another object of the invention is a process for the preparation of compounds of formula I
  • n 1, 2, 3 or 4
  • R n1 , R n2 , R n3 and R n4 is a radical other than hydrogen, selected from aryloxy, arylthio, hetaryloxy or hetarylthio,
  • n 1, 2, 3 or 4
  • R n1 , R n2 , R n3 and R n4 is a radical other than hydrogen, selected from aryloxy, arylthio, hetaryloxy or hetarylthio,
  • R a1 and R a2 are independently aryl
  • R b1 and R b2 are each independently alkyl, the compound of formula IV is subjected to a reaction with a strong Lewis acid and a proton donor, and wherein in the case where R b1 and R b2 are hydrogen the compound of formula IV is subjected to hydrogenolysis.
  • the invention also relates to novel compounds of general formula I, regardless of whether they are in the form of homo-aggregates or especially in the form of J-aggregates.
  • homo aggregates which are understood as supramolecular structures consisting exclusively of a compound of formula I. They differ from those of F. Würthner et al. in J. Am. Chem. Soc. 2004, 126, 1061 1-10618 described "Co" aggregates characterized by supramolecular co-self-organization of a p- and an n-type semiconductor.
  • the term "homo" aggregates refers to the molecular level.
  • z. B. in a solar cell according to the invention such a homo-aggregate with a suitable other material undergo a donor-acceptor interaction.
  • the formation of homo-aggregates or the avoidance of amorphous phases can take place for example by oswaldripening.
  • the compounds of the formula I are distinguished by their long-wave-shifted aggregate band, as has hitherto been unknown for prior art rylene dyes. Furthermore, the compounds of the formula I are distinguished by their strong long-wave fluorescence. They are thus suitable for. B. as an advantageous emitter in the near infrared range. Furthermore, their ability to form J-aggregates from compounds of the formula I is also surprising. This distinguishes them from the known co-aggregates in which excitonic dissociation takes place immediately in the coaggregates.
  • the compounds of the formula I thus, have properties such as specific emitter materials, charge transport materials or Excitontransportmaterialien z. B. in electroluminescence and photovoltaic applications are in demand.
  • J-aggregates result from a special packing in the aggregate, which leads to narrow absorption and emission bands, which are accompanied by a strong exciton delocalization.
  • Such aggregates are found in the natural light harvesting systems of plants and photochromic bacteria (see, for example, BT Pullerits, V. Sundström, Acc. Chem. Res. 1996, 29, 381-389 and TS Balaban, H. Tamiaki, AR Holzwarth, Top. Curr. Chem. 2005, 258, 1-38)
  • the compounds of the formula I used according to the invention as emitter materials, charge transport materials or exciton transport materials are at least 50% by weight, more preferably at least 75% by weight, in particular at least 90% by weight, especially 100% by weight. in the form of J-aggregates.
  • the compounds of the formula (I) are preferably used as n-semiconductors. However, in combination with certain other semiconductor materials, they can also be used as p-type semiconductors.
  • the organic semiconductor materials used according to the invention are particularly advantageous for use in solar cells. With solar cells based on these semiconductors, very good quantum yields can generally be achieved.
  • n denotes the number of naphthalene units linked in the peri-position, which form the skeleton of the rylene compounds according to the invention.
  • n denotes the particular naphthalene group of the rylene skeleton to which the radicals are bonded.
  • Radicals R n1 to R n4 which are bonded to different naphthalene groups may each have the same or different meanings.
  • the compounds of the general formula I may be naphthalene diimides, perylene diimides, terrylene diimides or Quaterrylene diimides act.
  • the structure concept is exemplified by the following preferred compounds.
  • radicals R n1 , R n2 , R n3 and R n4 are radicals other than hydrogen. 2 or 4 of the radicals R n1 , R n2 , R n3 and R n4 are particularly preferably radicals which are different from hydrogen.
  • n is 3 and 1, 2, 3 or 4 of the radicals R n1 , R n2 , R n3 and R n4 are radicals other than hydrogen. Particularly preferred are then 4 of the radicals R n1 , R n2 , R n3 and R n4 radicals other than hydrogen.
  • n is 4 and 1, 2, 3, 4, 5 or 6 of the radicals R n1 , R n2 , R n3 and R n4 are radicals other than hydrogen. Particularly preferred are then 4 or 6 of the radicals R n1 , R n2 , R n3 and R n4 radicals other than hydrogen.
  • alkyl includes straight-chain or branched alkyl. It is preferably straight-chain or branched C 1 -C 30 -alkyl, in particular C 1 -C 20 -alkyl and very particularly preferably C 1 -C 12 -alkyl.
  • alkyl groups are in particular methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1, 2-dimethylpropyl , 1, 1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2 , 3-dimethylbutyl, 1, 1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl 2-methylpropyl
  • alkyl also includes alkyl radicals whose carbon chains may be interrupted by one or more nonadjacent groups selected from -O-, -S-, -NR e -, -CO- and / or -SO 2 -.
  • R e is preferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • alkyl also includes substituted alkyl radicals.
  • Alkylene represents a linear saturated hydrocarbon chain having 1 to 10 and in particular 1 to 4 C atoms, such as ethane-1, 2-diyl, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5 diyl or hexane-1, 6-diyl.
  • cycloalkyl in the context of the present invention encompasses both unsubstituted and substituted cycloalkyl groups, preferably Cs-Cs-cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, in particular Cs-Cs-cycloalkyl.
  • the cycloalkyl groups may carry one or more, for example one, two, three, four or five substituents. These are preferably selected from C 1 -C 30 -alkyl groups.
  • Cs-Cs-cycloalkyl which is unsubstituted or may carry one or more C 1 -C 6 -alkyl groups is, for example, cyclopentyl, 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, cyclohexyl, 2-, 3- and 4- Methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 3- and 4-propylcyclohexyl, 3- and 4-isopropylcyclohexyl, 3- and
  • aryl in the context of the present invention comprises mononuclear or polynuclear aromatic hydrocarbon radicals which may be unsubstituted or substituted.
  • aryl preferably represents phenyl, ToIyI, XyIyI, mesityl, Duryl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl or naphthyl, particularly preferably phenyl or naphthyl, these aryl groups in the case of a substitution generally 1, 2, 3, 4 or 5, preferably 1, 2 or 3 substituents can carry.
  • substituents are preferably selected from C 1 -C 30 -alkyl, C 1 -C 30 -alkoxy, C 1 -C 8 -alkylthio, -C (OO) OR a , -OC (OO) R a , -C (OO) NR a R b , cyano, halo, aryl azo and heteroarylazo, wherein arylazo and heteroarylazo are in turn unsubstituted or may bear one or more radicals (eg 1, 2, 3, 4 or 5) which are independently selected from C 1 -C 30 -alkyl, C 1 -C 30 -alkoxy, C 1 -C 30 -alkylthio, cyano and halogen.
  • radicals eg 1, 2, 3, 4 or 5
  • R a and R b are preferably independently of one another hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • the radicals R a and R b may in turn be unsubstituted or may carry one or more radicals (eg 1, 2, 3, 4 or 5).
  • R a and R b which may be alkyl in the case of substitution generally have 1, 2, 3, 4 or 5, preferably carry 1, 2 or 3 substituents. These substituents are preferably selected from cyano and halogen.
  • Radicals R a and R b which are cycloalkyl, heterocycloalkyl, aryl or hetaryl may in the case of a substitution generally carry 1, 2, 3, 4 or 5, preferably 1, 2 or 3 substituents.
  • substituents are preferably selected from C 1 -C 30 -alkyl, Ci-C3o-alkoxy, Ci-C3o-alkylthio, cyano and halogen, in particular C4-C3o-alkyl, C 4 -C 3 O -alkoxy and C 4 -C 3 o-alkylthio.
  • heterocycloalkyl in the context of the present invention comprises non-aromatic, unsaturated or fully saturated, cycloaliphatic groups having generally 5 to 8 ring atoms, preferably 5 or 6 ring atoms, in which 1, 2 or 3 of the ring carbon atoms by heteroatoms, selected from Oxygen, nitrogen, sulfur and a group -NR C - are replaced and which is unsubstituted or substituted with one or more, for example 1, 2, 3, 4, 5 or 6 d-C ⁇ -alkyl groups.
  • heterocycloaliphatic groups are pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothiophenyl, dihydrothien-2 -yl, tetrahydrofuranyl, dihydrofuran-2-yl, tetrahydropy- ranyl, 1, 2-oxazolin-5-yl, 1, 3-oxazolin-2-yl and dioxanyl called.
  • heteroaryl in the context of the present invention includes unsubstituted or substituted, heteroaromatic, mononuclear or polynuclear groups containing in addition to carbon ring members 1, 2, 3 or 4 heteroatoms from the group oxygen, nitrogen or sulfur as ring members, preferably the groups Pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl, purinyl, indazolyl, benzotriazolyl, 1, 2,3-triazolyl, 1, 3,4-triazolyl and carbazolyl, these heterocycloaromatic groups in the case of a substitution generally 1, 2 or 3 substituents can carry.
  • the substituents are selected from C 1 -C 30 -alkyl, C 1 -C 30 -alkoxy, C 1 -C 30 -alkylthio, hydroxy, carboxy and cyano.
  • the substituents are preferably selected from C 4 -C 30 -alkyl, C 4 -C 30 -alkoxy and C 4 -C 30 -alkylthio.
  • 5- to 10-membered heterocycloalkyl or heteroaryl radicals containing, in addition to carbon ring members, one to three nitrogen atoms and optionally further heteroatoms selected as ring members under oxygen and sulfur are, for example, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imino dazolinyl, imidazolidinyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, piperidinyl, piperazinyl, oxazolyl, isooxazolyl, thiazolyl, isothiazolyl, indolyl, quinolinyl, isoquinolinyl or quinaldinyl.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Carboxymethyl 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 5-carboxypentyl, 6-carboxyhexyl, 8-carboxyctyl, 10-carboxydecyl, 12-carboxydodecyl and 14-carboxy-tetradecyl;
  • Sulfomethyl 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl, 6-sulfohexyl, 8-sulfooctyl, 10-sulfodecyl, 12-sulfododecyl and 14-sulfotetradecyl;
  • Carbamoyl methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, butylaminocarbonyl, pentylaminocarbonyl, hexylaminocarbonyl, heptylaminocarbonyl, octylaminocarbonyl, nonylaminocarbonyl, decylaminocarbonyl and phenylaminocarbonyl;
  • Aminosulfonyl N, N-dimethylaminosulfonyl, N, N-diethylaminosulfonyl, N-methyl-N-ethylaminosulfonyl, N-methyl-N-dodecylaminosulfonyl,
  • a diimide of the formula (IV) in which at least one of the radicals R n1 , R n2 , R n3 and R n4 is a radical which is different from hydrogen and is selected from Alkylamino, dialkylamino, aryloxy, arylthio, hetaryloxy or Heta- rylthio.
  • R n1 , R n2 , R n3 and R n4 is a radical other than hydrogen, selected from aryloxy, arylthio, hetaryloxy or hetarylthio ,
  • At least one of the radicals R n1 , R n2 , R n3 and R n4 has as structural element an aryloxy group or hetaryloxy group which bears at least 2 substituents each independently selected from C 4 -C 30 -alkyl, C 4 C3o-alkoxy and C4-C3o-alkylthio, wherein the alkyl radicals of the alkyl, alkoxy and alkylthio substituents may be interrupted by one or more non-adjacent oxygen atom (s).
  • substituents each independently selected from C 4 -C 30 -alkyl, C 4 C3o-alkoxy and C4-C3o-alkylthio
  • the alkyl radicals of the alkyl, alkoxy and alkylthio substituents may be interrupted by one or more non-adjacent oxygen atom (s).
  • Such compounds are new and also the subject of the invention.
  • At least one of the radicals R n1 , R n2 , R n3 and R n4 is then aryloxy, arylthio, hetaryloxy or hetarylthio which bears at least 2 substituents, each of which is independently selected from among
  • At least one of the radicals R n1 , R n2 , R n3 and R n4 is aryloxy, arylthio, hetaryloxy or hetarylthio and has as an additional structural element an aryl group or hetaryl group which carries at least 2 substituents, each independently are selected from among C 4 -C 3 O-alkyl, C 4 -C 3 o-alkoxy and C 4 -C 3 o-alkylthio, wherein the alkyl radicals of the alkyl, alkoxy and alkylthio substituents by one or more non-adjacent oxygen atom ( e) can be interrupted.
  • the additional aryl group or hetaryl group may be bonded directly or via a bridging group to the aryloxy, arylthio, hetaryloxy or het arylthio group.
  • R n1 , R n2 , R n3 and R n4 are the following:
  • # represents the point of attachment to the rylene skeleton
  • x is 2 or 3, where in the compounds of the formulas 11.10, 11.1 1 and 11.12 x stands for 2,
  • R 1 are each independently selected from C 4 -C 30 -alkyl, C 4 -C 3 O-
  • Alkoxy and C4-C3o-alkylthio wherein the alkyl chains of the alkyl, alkoxy and alkylthio substituents may be interrupted by one or more non-adjacent oxygen atom (s).
  • Arylene is preferably phenylene, particularly preferably 1, 4-phenylene.
  • the bridging group A preferably represents a bridging group (III)
  • # represents the point of attachment to the rylene skeleton.
  • the bridging group A particularly preferably represents a group of the formula (III.1))
  • radicals R n1 , R n2 , R n3 and R n4 are radicals of the formulas (II.A1) and (II.A2)
  • radicals R n1 , R n2 , R n3 and R n4 are furthermore radicals of the formulas (II.B1) and (II.B2)
  • a 1 is O or S and R 4 is -C 3 alkylthio or C o-4 is -C 3 -alkoxy is C 4 -C 3 -alkyl, C.
  • radicals R n1 , R n2 , R n3 and R n4 are furthermore radicals of the formulas (II.C1) and (II.C2)
  • a 1 is O or S and R 4 is -C 3 alkylthio or C o-4 is -C 3 -alkoxy is C 4 -C 3 -alkyl, C.
  • radicals of the formulas (II.C1) and (II.C2) are the groups
  • radicals R n1 , R n2 , R n3 and R n4 are furthermore radicals of the formulas (II.D1) and (II. D2)
  • a 1 is O or S and R 4 is -C 3 alkylthio or C o-4 is -C 3 -alkoxy is C 4 -C 3 -alkyl, C.
  • a 1 is O or S and R 4 is -C 3 alkylthio or C o-4 is -C 3 -alkoxy is C 4 -C 3 -alkyl, C.
  • 4,5,6-tri (n-butyl) -pyrimidin-2-yl, 4,5,6-tri (n-pentyl) -pyrimidin-2-yl, 4,5,6-tri (n-hexyl) -pyrimidin-2-yl, 4,5,6-tri (n-heptyl) -pyrimidin-2-yl, 4,5,6-tri (n-octyl) -pyrimidin-2-yl, 4,5,6 Tri (n-nonyl) -pyrimidin-2-yl, 4,5,6-trii (n-decyl) -pyrimidin-2-yl, 4,5,6-tri (n-undecy) -pyrimidine-2-yl yl, 4,5,6-tri (n-dodecyl) -pyrimidin-2-yl, 4,5,6-tri (n-tridecyl) -pyrimidin-2-yl, 4,5,6-tri (n
  • radicals R n1 , R n2 , R n3 and R n4 are furthermore radicals of the formulas (II.F1) and (II.F2) (II.F1) (II. F2)
  • a 1 is O or S and R 4 is -C 3 alkylthio or C o-4 is -C 3 -alkoxy is C 4 -C 3 -alkyl, C.
  • An example of a preferred compound is 1, 6,7,12-tetrakis (4- [3,4,5-tridodecyl-oxybenzoyloxy] phenoxy) perylene-3,4: 9,10-tetracarboxylic diimide (1):
  • the inventive and inventively used Rylenetetracarbonklare- diimides whose imide nitrogens carry hydrogen atoms, are usually capable of forming supramolecular structures in the form of self-assembled aggregates. This can be z. B. attributable to the ability of their imide groups to form hydrogen bonds. Surprisingly, this can lead to the formation of so-called J-aggregates or disk aggregates, which is particularly advantageous for use of these compounds in excitonic solar cells. J aggregates are characterized by highly bathchromically-shifted absorption and fluorescence bands with narrow bandwidths over monomer absorption, coupled with high fluorescence quantum efficiency. Their behavior is based on a strong intermolecular coupling of the electronic excitation associated with a high excitonic mobility. This is of paramount importance for effective use of incident light in excitonic solar cells.
  • FIG. 1 shows, by the example of (1), the arrangement of rylenetetracarboxylic diimides in J-type aggregates.
  • the arrows in image section A) symbolize hydrogen bonds.
  • Section B) shows the helical self-assembly of the rylenetetracarboxylic diimides (substituents were omitted and only the left-handed HeNx is reproduced).
  • Section C) shows an enlarged detail of a double strand of Rylenetetracarbonkladiimide with the J arrangement of the superimposed aggregates.
  • the rylenetetracarboxylic diimides according to the invention and those used according to the invention are self-complementary compounds because of their hydrogen-carrying imide nitrogens, ie they are capable, even in the absence of further compounds, of arranging themselves into chains along which excitons can migrate.
  • rylenetetracarboxylic diimides in which one or more of R n1 , R n2 , R n3 and R n4 is substituted or unsubstituted aryloxy, arylthio, hetarylo- xy or hetarylthio have a twisted ⁇ -conjugated core.
  • Rylenetetracarboxylic diimides according to the invention and used according to the invention with the ability to form superimposed molecular stacks with ⁇ - ⁇ interaction are characterized by a bathochromic shift compared with the monomeric compounds and exhibit excitonic fluorescence states.
  • the individual dimeric molecular stacks can form a tightly packed one-dimensional supramolecular polymer that has the typical properties of a J-aggregate.
  • the experimental detection of superimposed molecular stacks with ⁇ - ⁇ interaction is possible, for example, on the basis of the UVA / IS spectra.
  • the formation of hydrogen bonds (such as NH ⁇ ⁇ O bonds between imides and carbonyl nitrogens) can be detected by concentration- and temperature-dependent FT-IR spectroscopy and 1 H NMR.
  • the size and shape of the aggregates can be determined by atomic force microscopy (AFM). Information about the dynamics of excitons can be found eg. B. win with time-resolved fluorescence spectroscopy.
  • AFM atomic force microscopy
  • fluorescence lifetime is a sensitive parameter for describing molecular systems in their basic dynamic properties. From the decrease of the fluorescence lifetime from the monomer to the aggregate, the size of the coherent domain can be estimated in the absence of radiation-free quenching processes. This is z. B. for the compound (1) about three molecules at room temperature. At lower temperatures, a large increase in the size of the coherent domain can be expected.
  • the rylenetetracarboxylic diimides according to the invention and those used according to the invention are particularly advantageous for use in organic photovoltaics, in particular as semiconductors in excitonic solar cells.
  • R a1 and R a2 independently represent aryl and R b1 and R b2 independently represent alkyl, can easily undergo a reaction to give diimides (I) in which the imide nitrogens carry hydrogen atoms.
  • Another object of the invention is therefore a process for the preparation of compounds of formula I.
  • n 1, 2, 3 or 4
  • At least one of the radicals R n1 , R n2 , R n3 and R n4 is a radical which is different from hydrogen and is selected from aryloxy, arylthio, hetaryloxy or hetarylthio, in which a diimide of the formula (IV)
  • n 1, 2, 3 or 4
  • R n1 , R n2 , R n3 and R n4 have the meaning given above,
  • R a1 and R a2 are independently aryl
  • R b1 and R b2 are each independently alkyl, the compound of formula IV is subjected to a reaction with a strong Lewis acid and a proton donor, and wherein in the case where R b1 and R b2 are hydrogen the compound of formula IV is subjected to hydrogenolysis.
  • R a1 and R a2 preferably have the same meaning and, for example, both represent phenyl.
  • R b1 and R b2 preferably have the same meaning and are, for example, both C 1 -C 12 -alkyl, more preferably C 1 -C 12 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl.
  • R d1 and R d1 are both methyl.
  • R b1 and R b2 are preferably the same and, for example, both are hydrogen.
  • the deprotection is usually carried out under such reaction conditions as are known from the prior art for the removal of the respective protective group. Suitable deprotection methods are described, for example, in TW Greene, PGM Wuts, Protective Groups in Organic Synthesis, 3rd Edition, Wiley Interscience 1999, or PJ Kocienski, Protective Groups, Thieme 2000, incorporated herein by reference.
  • R b1 and R b2 are hydrogen
  • the cleavage of the benzyl moiety is preferably carried out by hydrogenolysis.
  • the hydrogenolysis is generally carried out under known conditions, for example using a suitable hydrogenation catalyst, such as palladium, palladium hydroxide or platinum.
  • R b1 and R b2 are each independently alkyl
  • the cleavage is carried out by treating the compound IV with a Lewis acid.
  • Covalent metal halides and semimetallic halides having an electron-pair gap may be considered as the Lewis acid.
  • Such compounds are known to the person skilled in the art, for example from JP Kennedy, B. Ivan, "Designed Polymers by Carbocationic Macromolecular Engineering", Oxford University Press, New York, 1991. They are usually selected from halogen compounds of titanium, tin, of aluminum, vanadium or iron, and in particular the halogen ides of boron.
  • Lewis acids are boron tribromide, boron trichloride, titanium tetra-chloride, tin tetrachloride, aluminum trichloride, vanadium pentachloride, iron trichloride, alkylaluminum dichlorides and dialkylaluminum chlorides.
  • Particularly preferred Lewis acids are boron tribromide and titanium tetrachloride.
  • the Lewis acid is employed in an amount sufficient to react both imide groups of the compound of formula IV.
  • the molar ratio of Lewis acid to compound of the formula IV is preferably 2: 1 to 10: 1 and more preferably 2.1: 1 to 5: 1.
  • Suitable solvents are those which are stable to Lewis acids.
  • Preferred solvents are halogenated hydrocarbons, e.g. As halogenated aliphatic hydrocarbons, especially haloalkanes, such as chloromethane, dichloromethane, trichloromethane, chloroethane, 1, 2-dichloroethane, 1, 1-trichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane and 2-chlorobutane, and halogenated aromatic hydrocarbons, such as chlorobenzene and fluorobenzene. Also suitable are mixtures of the abovementioned solvents. Particularly preferred solvents are the abovementioned haloalkanes, especially dichloromethane.
  • reaction is carried out initially under largely apro- tic, especially under anhydrous, reaction conditions.
  • the pre-cleaning or predrying of the solvent is carried out in the usual manner, preferably by treatment with solid drying agents such as molecular sieves or predried oxides such as alumina, silica, calcium oxide or barium oxide.
  • one will carry out the method according to the invention at temperatures ranging from 60 to -140 0 C, preferably in the range from 40 to -80 0 C, more preferably in the range from 25 to -40 0 C.
  • a protic compound (proton donor) is added to the reaction mixture.
  • the proton donor is preferably selected from water, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol or tert-butanol, or mixtures thereof with water. Particularly suitable are water / methanol and water / ethanol mixtures.
  • the isolation and optionally purification of the obtained diimide (I) is carried out by customary methods known to the person skilled in the art. This includes z. B. removing the solvent used for the reaction, for. B. by evaporation. The evaporation can be carried out under elevated temperature and / or reduced pressure. In a suitable embodiment, the solvent used for the reaction with the Lewis acid is partially or completely removed already before the addition of the proton donor. Isolation of diimide (I) may involve precipitation with a suitable precipitant. Preferably, a proton donor is used to release the diimide (I), in which the compound (I) is not or only slightly soluble. Such proton donors are water and water / alcohol mixtures with sufficient water content.
  • the isolation of diimide (I) may further comprise at least one filtration and / or drying step.
  • the aforementioned compounds may be subjected to further purification. These include, for example, column chromatographic methods, sublimation, crystallization or a combination of several of these methods.
  • column chromatography and the crystallization are each carried out using a suitable solvent. These include halogenated hydrocarbons, such as methylene chloride or chloroform, or aromatic solvents.
  • a suitable solvent include halogenated hydrocarbons, such as methylene chloride or chloroform, or aromatic solvents.
  • aprotic carboxylic acid amides if appropriate in combination with water and / or an alcohol, in order to reduce the solubility.
  • poorly soluble compounds can also be purified by fractionation from sulfuric acid.
  • the cleaning by sublimation can be carried out using a temperature gradient, for. In a 3-zone sublimation device.
  • the preparation of a perylene according to the invention is summarized in the following scheme using the example of 1,6,7,12-tetrakis (4- [3,4,5-tridodecyloxybenzoyloxy] phenoxy) perylene-3,4: 9,10-tetracarboxylic diimide (1) :
  • DMAP 4-Dimethylaminopyridine
  • DPTS 4- (dimethylamino) pyidinium-4-tosylate
  • MMF dimethylformamide
  • CH 2 Cl 2 from 0 0 C to 50 0 C within 91 h.
  • the compounds of the formula (I) are particularly advantageous for use in organic photovoltaics (OPV).
  • OCV organic photovoltaics
  • these compounds are suitable for use in dye-sensitized solar cells.
  • their use in solar cells which are characterized by a diffusion of excited states (exciton diffusion)
  • one or both of the semiconductor materials used is characterized by a diffusion of excited states (exciton mobility).
  • the combination of at least one semiconductor material which is characterized by a diffusion of excited states, with polymers which allow conduction of the excited states along the polymer chain.
  • Such solar cells are referred to as excitonic solar cells within the meaning of the invention. Direct conversion of solar energy into electrical energy in solar cells relies on the internal photoelectric effect of a semiconductor material, i.
  • H the generation of electron-hole pairs by absorption of photons and the separation of the negative and positive charge carriers at a p-n junction or a Schottky contact.
  • An exciton can z. B. arise when a photon penetrates into a semiconductor and an electron to excite the transition from the valence band in the conduction band.
  • the excited state created by the absorbed photons must reach a p-n junction to create a hole and an electron, which then flows to the anode and cathode.
  • the photovoltaic voltage thus generated can cause a photocurrent in an external circuit, through which the solar cell gives off its power. In this case, only those photons can be absorbed by the semiconductor, which have an energy that is greater than its band gap.
  • the size of the semiconductor band gap thus determines the proportion of sunlight that can be converted into electrical energy.
  • the described excitonic solar cells usually consist of two absorbing materials with different band gaps in order to use the solar energy as effectively as possible.
  • Most organic semiconductors have exciton diffusion lengths of up to 10 nm.
  • Suitable organic solar cells are generally layered and generally comprise at least the following layers: anode, photoactive layer and cathode. These layers are usually on a conventional substrate.
  • the structure of organic solar cells is z. B. in US 2005/0098726 A1 and US 2005/0224905 A1, which is incorporated herein by reference.
  • Suitable substrates are for. Oxidic materials (such as glass, quartz, ceramics, SiO 2, etc.), polymers (e.g., polyvinyl chloride, polyolefins such as polyethylene and polypropylene, polyesters, fluoropolymers, polyamides, polyurethanes, polyalkyl (meth) acrylates, polystyrene and blends and composites thereof) and combinations thereof.
  • Oxidic materials such as glass, quartz, ceramics, SiO 2, etc.
  • polymers e.g., polyvinyl chloride, polyolefins such as polyethylene and polypropylene, polyesters, fluoropolymers, polyamides, polyurethanes, polyalkyl (meth) acrylates, polystyrene and blends and composites thereof.
  • metals preferably groups 8, 9, 10 or 11 of the Periodic Table, eg Pt, Au, Ag, Cu, Al, In, Mg, Ca
  • semiconductors eg. Doped Si, doped Ge, indium tin oxide (ITO), gallium indium tin oxide (GITO), zinc indium tin oxide (ZITO), etc.
  • metal alloys eg Based on Pt, Au, Ag, Cu, etc., especially Mg / Ag alloys
  • the anode used is a material that is substantially transparent to incident light. This includes z. ITO, doped ITO, ZnO, TiO 2, Ag, Au, Pt.
  • the cathode used is preferably a material that essentially reflects the incident light. These include z. As metal films, z. B. from Al, Ag, Au, In, Mg, Mg / Al, Ca, etc.
  • the photoactive layer in turn comprises at least one or consists of at least one layer which contains as organic semiconductor material at least one compound which is selected from compounds of the formulas I and II, as defined above.
  • the photoactive layer comprises at least one organic acceptor material.
  • there may be one or more further layers e.g. for example, a layer with electron-conducting properties (ETL) and a layer containing a hole-transporting material (HTL) that need not absorb, excitons and hole-blocking layers (eg excitation blocking layers, EBL) that are not supposed to absorb multiplication layers. Suitable excitons and holes blocking layers are z. As described in US 6,451, 415.
  • Suitable Excitonenblocker für z. B. Bathocuproine (BCP), 4,4 ', 4 "-Tris (N- (3-methylphenyl) -N-phenylamino) triphenylamine (m-MTDATA) or polyethylenedioxithiophene (PEDOT), as described in US 7,026,041.
  • the excitonic solar cells according to the invention are based on photoactive donor-acceptor heterojunctions. If at least one compound of the formula (I) is used as HTM, the corresponding ETM must be selected such that a rapid electron transfer to the ETM takes place after excitation of the compounds. Suitable ETMs are z. B. C60 and other fullerenes, perylene-3,4: 9,10-bis (dicarboximides)
  • the complementary HTM must be chosen such that after excitation of the compound rapid hole transfer to the HTM takes place.
  • the heterojunction can be carried out flatly (compare Two layer organic photovoltaic cell, CW Tang, Appl. Phys. Lett, 48 (2), 183-185 (1986) or N. Karl, A. Bauer, J. Holzäpfel, J. Cryst., Liq., Cryst, 252, 243-258 (1994).) Or as a bulk heterojunction or interpenetrated donor-acceptor network, cf. BCJ Brabec, NS Sariciftci, JC Hummelen, Adv. Funct.
  • Thin layers of the compounds and of all other layers can be obtained by vapor deposition in a vacuum or inert gas atmosphere, by laser ablation or by solution or dispersion processable methods such as spin coating, knife coating, casting, spraying, dip coating or printing (eg InkJet, Flexo , Offset, gravure, gravure, nanoimprint).
  • the layer thicknesses of the M, n, i and p layers are typically 10 to 1000 nm, preferably 10 to 400 nm.
  • a substrate z As a substrate z.
  • metal or polymer films are used, which are usually coated with a transparent, conductive layer (such as Sn ⁇ 2: F, Sn ⁇ 2: In, ZnO: Al, carbon nanotubes, thin metal layers).
  • a transparent, conductive layer such as Sn ⁇ 2: F, Sn ⁇ 2: In, ZnO: Al, carbon nanotubes, thin metal layers.
  • Acenes such as anthracene, tetracene, pentacene, which may each be unsubstituted or substituted.
  • Substituted acenes preferably comprise at least one substituent selected from electron-donating substituents (eg, alkyl, alkoxy, ester, carboxylate or thioalkoxy), electron-withdrawing substituents (eg, halogen, nitro, or cyano), and combinations thereof.
  • electron-donating substituents eg, alkyl, alkoxy, ester, carboxylate or thioalkoxy
  • electron-withdrawing substituents eg, halogen, nitro, or cyano
  • Suitable substituted pentacenes are described in US 2003/0100779 and US Pat. No. 6,864,396, which is hereby incorporated by reference. train is taken.
  • a preferred acene is rubrene (5,6,11,12-tetraphenylnaphthacene);
  • Phthalocyanines for example phthalocyanines which carry at least one halogen substituent, such as hexadecachlorophthalocyanines and hexadecafluorophthalocyanines, phthalocyanines containing metal-free or divalent metals or metal atom-containing groups, in particular those of titanyloxy, vanadyloxy, iron, copper, zinc, etc.
  • Suitable phthalocyanines are in particular copper phthalocyanine, zinc phthalocyanine, metal-free phthalocyanine, hexadecachloro copper phthalocyanine, hexadecochlorozinc phthalocyanine, metal-free hexadecachlorophatho-cyanine, hexadecafluoro copper phthalocyanine, hexadecafluorophthalocyanine or metal-free hexafluorophthalocyanine;
  • Porphyrins such as. 5,10,15,20-tetra (3-pyridyl) porphyrin (TpyP);
  • Liquid crystalline (LC) materials for example, coronene such as hexabenzocoronene
  • HAT6 2,3,6,7,10,1 1-hexahexylthiotriphenylene
  • PTP9 2,3,6,7,10,11-hexakis- (4-n-nonylphenyl) -triphenylene
  • HAT11 2,3 , 6,7,10,11-Hexakis (undecyloxy) -triphenylene
  • liquid crystalline materials that are discotic;
  • oligothiophenes are quaterthiophenes, quinquethiophenes, sexithiophenes, ⁇ , ⁇ -di (C 1 -C 8) -alkyloligothiophenes, such as ⁇ , ⁇ -dihexylquaterthiophenes, ⁇ , ⁇ -dihexylquinquethiophenes and ⁇ , ⁇ -dihexylsexithiophenes, poly (alkylthiophenes), such as poly (3-hexylthiophene), bis (dithienothiophenes), anthradithiophenes, and dialkylanthra-dithiophenes such as dihexylanthradithiophene, phenylene-thiophene (PT) oligomers, and derivatives thereof, especially ⁇ ,
  • DCV5T compounds of the type ⁇ , ⁇ '-bis (2,2-dicyanovinyl) quinquethiophene
  • Paraphenylenevinylene and paraphenylenevinylene containing oligomers or polymers such.
  • Phenylenethinylene / phenylenevinylene hybrid polymers (PPE-PPV);
  • Polycarbazoles d. H. Carbazole containing oligomers and polymers such as (2,7) and (3,6).
  • Polyanilines d. H. Aniline-containing oligomers and polymers such as (2,7) and (3,6).
  • Triarylamines polytriarylamines, polycyclopentadienes, polypyrroles, polyfurans, polysiols, polyphospholes, TPD, CBP, spiro-MeOTAD.
  • the fullerene derivative is a hole conductor.
  • p-n mixed materials d. H. Donor and acceptor in one material, polymer, block polymer, polymers with C60s, C60 azo dyes, triads carotenoid porphyrin quinode LC donor / acceptor systems as described by Kelly in S. Adv. Mater. 2006, 18, 1754.
  • All of the aforementioned semiconductor materials may also be doped.
  • Examples of dopants for p-type semiconductor 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F 4 -TCNQ), etc.
  • the (novel) compounds (I) according to the invention are also particularly advantageously suitable as organic semiconductors. They usually act as n-semiconductors. If the compounds of the formula (I) used in accordance with the invention are combined with other semiconductor conductors and if the position of the energy levels results in the other semiconductors functioning as n-type semiconductors, the compounds (I) can also function as p-type semiconductors by way of exception. This is z. As in the combination with cyano-substituted perylenetetracarboximides the case.
  • the compounds of the formula (I) are distinguished by their air stability. Furthermore, they have a high charge transport mobility and have a high on / off ratio. They are particularly suitable for organic field effect transistors.
  • the compounds according to the invention are advantageously suitable for the production of integrated circuits (ICs), for hitherto common n-channel MOSFETs (MOSFETs) are used, which are CMOS analog semiconductor devices, eg for microprocessors, microcontrollers, static RAM, and other digital logic devices.
  • ICs integrated circuits
  • MOSFETs hitherto common n-channel MOSFETs
  • the processes according to the invention can be further processed by one of the following processes: printing (offset, flexo, gravure, screen, inkjet, electrophotography), evaporation, laser transfer, photolithography, dropcasting, etc. They are particularly suitable for use in displays (especially large and / or flexible displays) and RFI D tags.
  • the compounds according to the invention are furthermore particularly advantageously suitable for data storage in diodes, especially in OLEDs, in photovoltaics, as UV absorbers, as optical brighteners, as invisible labels and as fluorescent labels for biomolecules, such as proteins, DNA, sugars and combinations thereof.
  • the compounds according to the invention are furthermore particularly advantageously suitable as fluorescent dye in a display based on fluorescence conversion; in a light-collecting plastic part, which is optionally combined with a solar cell; as a pigment in electrophoretic displays; as a fluorescent dye in a chemiluminescence-based application (eg in glow sticks).
  • the compounds according to the invention are furthermore particularly advantageously suitable as fluorescent dye in a display based on fluorescence conversion.
  • Such displays generally include a transparent substrate, a fluorescent dye on the substrate, and a radiation source.
  • Common sources of radiation emit blue (color-by-blue) or UV (color-by-UV) light.
  • the dyes absorb either the blue or the UV light and are used as a green emitter.
  • B. the red light is generated by the red emitter is excited by a blue or UV light-absorbing green emitter.
  • Suitable color-by-blue displays are z.
  • Suitable color-by-uv displays are z.
  • the compounds according to the invention are furthermore particularly suitable as fluorescence emitters in OLEDs in which they are excited either by electroluminescence or by a corresponding phosphorescence emitter via Förster energy transfer (FRET).
  • FRET Förster energy transfer
  • the compounds according to the invention are furthermore particularly suitable in displays which turn colors on and off based on an electrophoretic effect via charged pigment dyes. Such electrophoretic displays are z. As described in US 2004/0130776.
  • the compounds according to the invention are furthermore particularly suitable for use in a light-collecting plastic part which absorbs light over a large area and emits light at its edges after repeated refraction (so-called LISAs). Such LISAs can be used on the edges of solar cells such. As silicon solar cells or organic solar cells, which convert the concentrated light into electrical energy. A combination of light-collecting plastics with solar cells is z. As described in US 4,110,123.
  • the compounds according to the invention are furthermore particularly suitable in chemoluminescence applications. These include so-called "Glow Sticks".
  • Glow Sticks For their preparation, at least one compound of formula (I) z. B. are dissolved in an alkyl phthalate.
  • An excitation of chemiluminescence can be done by mixing an oxalic acid ester with hydrogen peroxide, for. B. after these two initially separate components are mixed by breaking a glass. The resulting reaction energy leads to the excitation and fluorescence of the dyes.
  • glow sticks can be used as emergency light, z. B. used in fishing, life-saving vests or other security applications.
  • the invention furthermore relates to organic field-effect transistors, comprising a substrate having at least one gate structure, a source electrode and a drain electrode and at least one compound of the formula I, as defined above, as n-type semiconductor.
  • the invention further substrates with a plurality of organic field effect transistors, wherein at least a portion of the field effect transistors contains at least one compound of formula I, as defined above, as n-type semiconductor.
  • the invention also relates to semiconductor devices which comprise at least such a substrate.
  • a particular embodiment is a substrate having a pattern (topography) of organic field effect transistors, each transistor
  • an organic semiconductor on the substrate a gate structure for controlling the conductivity of the conductive channel; and conductive source and drain electrodes at both ends of the channel
  • the organic semiconductor consists of at least one compound of the formula (I) or comprises a compound of the formula (I). Furthermore, the organic field effect transistor usually comprises a dielectric.
  • Another specific embodiment is a substrate having a pattern of organic field effect transistors, each transistor forming an integrated circuit. or part of an integrated circuit and wherein at least part of the transistors comprises at least one compound of formula (I).
  • Suitable substrates are in principle the known materials.
  • Suitable substrates include, for. Metals (preferably metals of Groups 8, 9, 10 or 11 of the Periodic Table such as Au, Ag, Cu), oxidic materials (such as glass, quartz, ceramics, SiO 2), semiconductors (eg doped Si, doped Ge), metal alloys (eg based on Au, Ag, Cu, etc.), semiconductor alloys, polymers (eg polyvinyl chloride, polyolefins, such as polyethylene and polypropylene, polyesters, fluoropolymers, polyamides, polyimides , Polyurethanes, polyalkyl (meth) acrylates, polystyrene, and mixtures and composites thereof), inorganic solids (eg, ammonium chloride), paper, and combinations thereof.
  • the substrates can be flexible or inflexible solid, with curved or planar geometry, depending on the desired application.
  • a typical substrate for semiconductor devices comprises a matrix (eg, a quartz or polymer matrix) and, optionally, a dielectric capping layer.
  • a matrix eg, a quartz or polymer matrix
  • a dielectric capping layer e.g., a dielectric capping layer
  • Suitable dielectrics are SiO 2, polystyrene, poly- ⁇ -methylstyrene, polyolefins (such as polypropylene, polyethylene, polyisobutene) polyvinylcarbazole, fluorinated polymers (eg Cytop, CYMM) cyanopullanes, polyvinylphenol, poly-p-xylene, polyvinylchloride or thermally or by Humidity crosslinkable polymers.
  • Special dielectrics are "seif assembled nanodielectrics", ie polymers derived from SiCI functionalities containing monomers such.
  • CI 3 SiOSiCI 3 CI 3 Si (CH 2 ⁇ -SiCI 3 , CI 3 Si (CH 2 ) ⁇ - SiCl 3 and / or which are crosslinked by atmospheric moisture or by the addition of water in dilution with solvents ( See, for example, Faccietti Adv. Mat., 2005, 17, 1705-1725.)
  • water it is also possible to use hydroxyl-containing polymers such as polyvinylphenol or polyvinyl alcohol or copolymers of vinylphenol and styrene as crosslinking components
  • Crosslinking process such as polystyrene, which is then crosslinked (see Facietti, US patent application 2006/0202195).
  • the substrate may additionally include electrodes, such as gate, drain, and source electrodes of OFETs, which are normally located on the substrate (eg, deposited on or embedded in a nonconductive layer on the dielectric).
  • the substrate may additionally include conductive gate electrodes of the OFETs, which are typically disposed below the dielectric capping layer (i.e., the gate dielectric).
  • an insulator layer (gate insulating layer) is located on at least one part of the substrate surface.
  • the insulator layer comprises at least one insulator which is preferably selected from inorganic insulators such as SiO 2 , SiN, etc., ferroelectric insulators such as Al 2 O 3 , Ta 2 Os, La 2 Os, TiO 2 , Y2O3, etc., organic insulators such as polyimides, benzocyclobutene (BCB), polyvinyl alcohols, polyacrylates, etc., and combinations thereof.
  • inorganic insulators such as SiO 2 , SiN, etc.
  • ferroelectric insulators such as Al 2 O 3 , Ta 2 Os, La 2 Os, TiO 2 , Y2O3, etc.
  • organic insulators such as polyimides, benzocyclobutene (BCB), polyvinyl alcohols, polyacrylates, etc., and combinations thereof.
  • drain and source electrodes are at least partially on the organic semiconductor material.
  • the substrate may include other components, such as are commonly used in semiconductor materials or ICs, such as insulators, resistors, capacitors, interconnects, etc.
  • the electrodes can be applied by conventional methods such as evaporation, lithographic methods or another patterning process.
  • the semiconductor materials can also be processed with suitable auxiliaries (polymers, surfactants) in disperse phase by printing.
  • the deposition of at least one compound of general formula I (and optionally other semiconductor materials) by a vapor deposition method Physical Vapor Deposition PVD.
  • PVD processes are performed under high vacuum conditions and include the following steps: evaporation, transport, deposition.
  • the compounds of the general formula I are particularly advantageous for use in a PVD process, since they do not substantially decompose and / or form undesired by-products.
  • the deposited material is obtained in high purity. In a specific embodiment, the deposited material is obtained in the form of crystals or contains a high crystalline content.
  • At least one compound of general formula I is heated to a temperature above its vaporization temperature for PVD and deposited on a substrate by cooling below the crystallization temperature.
  • the temperature of the substrate in the deposition is preferably in a range of about 20 to 250 0 C, more preferably 50 to 200 0 C.
  • increased substrate temperatures in the deposition of the compounds of the formula I advantageous effects on the properties the achieved semiconductor elements can have.
  • the resulting semiconductor layers generally have a thickness sufficient for an ohmic contact between the source and drain electrodes.
  • the deposition may be carried out under an inert atmosphere, e.g. B. under nitrogen, argon or helium.
  • the deposition is usually carried out at ambient pressure or under reduced pressure.
  • a suitable pressure range is about 10 " 7 to 1, 5 bar.
  • the compound of formula (I) is deposited on the substrate in a thickness of 10 to 1000 nm, more preferably 15 to 250 nm.
  • the compound of the formula I is deposited at least partially in crystalline form.
  • the PVD method described above is suitable.
  • Preferred solvents for the use of the compounds of the formula (I) in a printing process are aromatic solvents, such as toluene, xylene, etc. It is possible to add thickening substances, such as polymers, to these "semicontrinates", eg. As polystyrene, etc. It uses as a dielectric, the aforementioned compounds.
  • the field effect transistor according to the invention is a thin film transistor (TFT).
  • TFT thin film transistor
  • a thin film transistor has a gate electrode disposed on the substrate, a gate insulating layer disposed thereon and the substrate, a semiconductor layer disposed on the gate insulating layer, an ohmic contact layer on the semiconductor layer, and a source electrode and a drain electrode on the ohmic contact layer.
  • the surface of the substrate is deposited prior to the deposition of at least one compound of general formula (I) (and given if at least one further semiconductor material) undergoes a modification.
  • This modification serves to form regions that bond the semiconductor materials and / or regions where no semiconductor materials can be deposited.
  • the surface of the substrate is modified with at least one compound (C1) which is suitable for bonding to the surface of the substrate as well as the compounds of the formula (I).
  • a part of the surface or the complete surface of the substrate is coated with at least one compound (C1) in order to allow an improved deposition of at least one compound of the general formula (I) (and optionally other semiconducting compounds).
  • Another embodiment comprises depositing a pattern of compounds of the general formula (C1) on the substrate according to a corresponding production method.
  • These include the well-known mask processes as well as so-called “patterning” method, as z.
  • patterning As described in US 1 1/353934, which is incorporated herein by reference in its entirety.
  • Suitable compounds of the formula (C1) are capable of a binding interaction both with the substrate and with at least one semiconductor compound of the general formula I.
  • binding interaction includes the formation of a chemical bond (covalent bond), ionic bond, coordinate interaction, Van der Waals interactions, e.g. Dipole-dipole interactions) etc. and combinations thereof.
  • Suitable compounds of the general formula (C1) are:
  • Silanes phosphonic acids, carboxylic acids, hydroxamic acids, such as Alkyltrichlorsila- ne, z. B. n- (octadecyl) trichlorosilane; Compounds with trialkoxysilane groups, e.g. B.
  • alkyltrialkoxysilanes such as n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltri- (n-propyl) oxysilane, n-octadecyltri- (isopropyl) oxysilane; Tri- alkoxyaminoalkylsilanes such as triethoxyaminopropylsilane and N [(3-triethoxysilyl) -propyl] -ethylenediamine; Trialkoxyalkyl 3-glycidyl ether silanes such as triethoxypropyl 3-glycidyl ether silane; Trialkoxyallylsilanes such as allyltrimethoxysilane; trialkoxy
  • Amines, phosphines and sulfur-containing compounds especially thiols.
  • the compound (C1) is selected from alkyltrialkoxysilanes, especially n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane; Hexaalkyldisilazanes, and especially hexamethyldisilazanes (HMDS); Cs-Cso-alkylthiols, especially hexadecanethiol; Mercaptocarboxylic acids and mercaptosulfonic acids especially mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, 3-mercapto-1-propanesulfonic acid and the alkali metal and ammonium salts thereof.
  • alkyltrialkoxysilanes especially n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane
  • Hexaalkyldisilazanes and especially
  • the layer thicknesses are in semiconductors z. B. 10 nm to 5 microns, the dielectric 50 nm to 10 microns, the electrodes may, for. B. 20 nm to 1 micron thick.
  • the OFETs can also be combined to other components such as ring oscillators or inverters.
  • Another aspect of the invention is the provision of electronic components comprising a plurality of semiconductor components, which may be n- and / or p-type semiconductors.
  • semiconductor components which may be n- and / or p-type semiconductors.
  • FETs field effect transistors
  • BJTs bipolar junction transistors
  • tunnel diodes inverters
  • light emitting devices biological and chemical detectors or sensors
  • temperature dependent detectors temperature dependent detectors
  • photodetectors such as polarization sensitive photodetectors, gates, AND, NAND , NOT, OR, TOR, and NOR gates, registers, switches, time blocks, static or dynamic memories, and other dynamic or sequential logical or other digital components, including programmable circuits.
  • a special semiconductor element is an inverter.
  • the inverter In digital logic, the inverter is a gate that inverts an input signal.
  • the inverter is also called NOT-gate.
  • Real inverter circuits have an output current that is the opposite of the input current. Usual values are z. (0, + 5V) for TTL circuits.
  • the performance of a digital inverter reflects the Voltage Transfer Curve (VTC); H. the order of input current versus output current. Ideally, it is a step function, and the closer the real measured curve approaches to such a step, the better the inverter.
  • VTC Voltage Transfer Curve
  • H the order of input current versus output current. Ideally, it is a step function, and the closer the real measured curve approaches to such a step, the better the inverter.
  • the compounds of the formula (I) are used as organic n-semiconductors in an inverter.
  • the suspension was stirred under argon atmosphere at room temperature for 70 h and at 50 ° C. for 21 h. After cooling to room temperature, 20 ml of water and 40 ml of CH 2 Cl 2 were added to the reaction mixture. The molecular sieve was then filtered off, the organic phase separated and the aqueous phase extracted three times with 30 ml CH 2 Cl 2. From the combined organic phases, the solvent was removed under reduced pressure and the residue was purified twice by column chromatography (silica gel, ChbCb / methanol (gradient 100: 0 to 99.5: 0.5 and then 99: 1)).
  • FIG. 2 shows the UV / VIS spectrum (line a) and the fluorescence spectrum (h line b) in CH 2 Cl 2 (10 ⁇ M) and the UV / VIS spectrum (line c) and the fluorescence spectrum (line d) in methylcyclohexane (10 ⁇ M) ).
  • the UV / VIS absorption spectrum and the fluorescence spectrum in CH2CI2 show the typical features of a perylene bisimide chromophore.
  • the UV / VIS absorption spectrum and the fluorescence spectrum of the aggregates present in the polar solvent methylcyclohexane differ greatly from the spectra of the monomeric compound. They show a strong bathochromic shift and unusually narrow bands of intense intensity.
  • Atomic force microscopy AFM (atomic force microscopy) measurements were performed under normal conditions with a Veeco MultiMode TM Nanoscope IV system in air tapping mode.
  • Silicon cantilevers (Olympus, OMCL-AC160TS) with a resonant frequency of ⁇ 300 kHz were used.
  • the 512x512 pixel images were recorded at a scan rate of 2 lines per second.
  • Solutions of (1) in methylcyclohexane were spin-coated onto highly oriented pyrolytic graphite (HOPG, NanoTechnology Instruments, Netherlands) (60 ⁇ M, 4000 rpm) or silicon wafers (NanoWorld AG, Switzerland) (9 ⁇ M, 2000 rpm).
  • Figure 3 shows AFM plots of monolayers of (1) adsorbed at the basal plane of HOPG by spincoating (4000 rpm) from MCH solution (60 ⁇ M).
  • a cross-sectional analysis showed an average thickness of 0.3 ⁇ 0.1 nm and a width of 5.7 ⁇ 0.2 nm for the aligned rows. The scaling is 45 nm, z-axis (A): 1, 5 nm, (B): 2.0 nm.
  • AFM studies with solutions of (1) in toluene and CCU gave comparable results.
  • Partial figures (C and D) show tapping-mode AFM representations of the self-assembly of (1) on silicon wafers.
  • the application was carried out by (2000 rpm) a 9 ⁇ M solution in MCH.
  • the scaling (white lines in the lower right corner of the image) corresponds to 300 nm, the z-scale is 6 nm.
  • Figure (E) shows an enlarged detail of (D).
  • the scaling (white line in the lower right corner) is 45 nm.
  • Figure (F) shows a model of the aggregate, where p is the helical pitch.
  • the half pitch distance p / 2 was determined to be 6.5 ⁇ 1.7 nm. This is in good agreement with the calculated value of 6 nm.
  • FIG. 4 shows concentration-dependent UV / Vis spectra of (1) (1.1 ⁇ M to 14 mM) in toluene at room temperature.
  • Small picture change in the extinction coefficient at 639 nm ( ⁇ ) and regression line according to an isodesmic or equal K model. The deviation of the calculated line from the measured ⁇ vs concentration values suggests a strong orientation across hydrogen bonds with ⁇ - ⁇ stacks.
  • Figure 5 shows STM plots of (1) adsorbed at the basal plane of HOPG by spincoating (4000 rpm) from MCH solution (60 ⁇ M).
  • the scaling is 20 nm, z-axis: 0.7 nm.
  • Figure (C) is an enlarged and filtered section of (B), the scaling is 20 nm.
  • D shows the molecular structure and arrangement of (1) on a unit cell as depicted in the STM plot.

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Abstract

La présente invention concerne un procédé de production de diimides de l'acide rylène-tétracarboxylique, dont les azotes imidés portent des atomes d'hydrogène, ainsi que leur utilisation, en particulier comme semiconducteurs organiques dans des cellules solaires excitoniques.
PCT/EP2008/053063 2007-03-16 2008-03-14 Procédé de production de diimides de l'acide rylène-tétracarboxylique, dont les azotes imidés portent des atomes d'hydrogène, et leur utilisation WO2008113753A1 (fr)

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Publication number Priority date Publication date Assignee Title
US8674104B2 (en) 2007-08-17 2014-03-18 Basf Se Halogen-containing perylenetetracarboxylic acid derivatives and the use thereof

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