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WO2009000831A1 - Dérivés d'acide rylène tétracarboxylique substitués par brome et leur utilisation - Google Patents

Dérivés d'acide rylène tétracarboxylique substitués par brome et leur utilisation Download PDF

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WO2009000831A1
WO2009000831A1 PCT/EP2008/058011 EP2008058011W WO2009000831A1 WO 2009000831 A1 WO2009000831 A1 WO 2009000831A1 EP 2008058011 W EP2008058011 W EP 2008058011W WO 2009000831 A1 WO2009000831 A1 WO 2009000831A1
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formula
compounds
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cyano
halogen
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Martin KÖNEMANN
Gabriele Mattern
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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
    • 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 bromine substituted, especially perbrominated, rylenetetracarboxylic acid derivatives and their use as emitter materials, charge transport materials or exciton transport materials.
  • organic semiconductors based on low-molecular or polymeric materials will increasingly be used in addition to the classical inorganic semiconductors.
  • These have many advantages over the classical inorganic semiconductors, for example a better substrate compatibility and a better processability of the semiconductor components based on them. They allow processing on flexible substrates and make it possible to precisely adapt their frontier orbital energies to the respective field of application using the methods of modular modeling. The significantly reduced cost of such components has brought a renaissance to the field of organic electronics research.
  • Organic Electronics "focuses on the development of new materials and manufacturing processes for the fabrication of electronic devices based on organic semiconductor layers, including organic field-effect transistors (OFETs) and organic light-emitting diodes (organic light-emitting diodes).
  • organic light-emitting diodes (OLEDs) and photovoltaics are attributed a great development potential, for example in memory elements and integrated optoelectronic devices
  • OLEDs organic light-emitting diodes
  • the property of materials is used to emit light as they pass through OLEDs are of particular interest as an alternative to cathode ray tubes and liquid crystal displays for the production of flat screens, because of their very compact design and intrinsic never Drigeren power consumption are suitable devices that contain OLEDs, especially for mobile applications, for example for applications in mobile phones, laptops, etc.
  • R 1 , R 2 , R 3 or 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 independently of one another are 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 or 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 , where 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,
  • perbrominated rylenetetracarboxylic acid derivatives of formula I described below are particularly advantageously suitable as emitter materials, charge transport materials or exciton transport materials. They are characterized in particular as air-stable n-type semiconductors with extraordinarily high charge mobilities.
  • a first subject of the present invention therefore relates to compounds of general formula I,
  • n 2, 3 or 4
  • R n1 , R n2 , R n3 and R n4 are halogen or cyano and especially bromine, where at least one of R n1 , R n2 , R n3 or R n4 is bromine,
  • 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 , Z 2 , Z 3 and Z 4 are O
  • one of the radicals Z 1 or 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 or 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 flanking bonds stand.
  • Another object of the invention relates to the use of the compounds of formula I as emitter materials, charge transport materials or Excitetonransport- materials.
  • 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. Accordingly, the compounds of general formula I may be perylenes, terrylenes or quaterrylenes of the following formulas:
  • 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, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl , n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl.
  • R e is preferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • alkyl also includes substituted alkyl radicals. Substituted alkyl groups may have one or more (eg 1, 2, 3, 4, 5 or more than 5) substituents depending on the length of the alkyl chain.
  • cycloalkyl preferably selected independently from among cycloalkyl, heterocycloalkyl, aryl, hetaryl, halogen, hydroxy, mercapto (-SH), COOH, carboxylate, SO 3 H, sulfonate, NE 1 E 2 , nitro and cyano, wherein E 1 and E 2 independently of one another represent hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • Halogen substituents are preferably fluorine, chlorine or bromine.
  • Alkylene is divalent straight or branched hydrocarbon radicals having usually 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms and especially 1 to 12 carbon atoms.
  • Carboxylate and sulfonate represent a derivative of a carboxylic acid function or a sulfonic acid function, in particular a metal carboxylate or sulfonate, a carboxylic acid ester or sulfonic acid ester function or a carboxylic acid or sulfonic acid amide function.
  • Cycloalkyl, heterocycloalkyl, aryl and hetaryl substituents of the alkyl groups may themselves be unsubstituted or substituted; suitable substituents are those mentioned below for these groups.
  • alkyl also apply to the alkyl moieties in alkoxy, alkylamino, alkylthio, alkylsulfinyl, alkylsulfonyl, etc.
  • Aryl substituted alkyl (“arylalkyl”) groups have at least one unsubstituted or substituted aryl group as defined below.
  • the alkyl group in "arylalkyl” may carry at least one further substituent and / or may be substituted by one or more nonadjacent groups which are selected from -O-, -S-, -NR e -, -CO- and / or - SO2 be interrupted.
  • Arylalkyl is preferably phenyl-Ci-Cio-alkyl, particularly preferably phenyl-Ci-C4-alkyl, for.
  • benzyl 1-phenethyl, 2-phenethyl, 1-phenprop-1-yl, 2-phenprop-1-yl, 3-phenprop-1-yl, 1-phenbut-1-yl, 2-phenbut-1 -yl, 3-phenbut-1-yl, 4-phenbut-1-yl, 1-phenbut-2-yl, 2-phenbut-2-yl, 3-phenbut-2-yl, 4-phenbut-2-yl , 1- (phenmeth) eth-1-yl,
  • alkenyl in the context of the present invention comprises straight-chain and branched alkenyl groups which, depending on the chain length, may carry one or more double bonds (eg 1, 2, 3, 4 or more than 4). Preference is given to C 2 -C 18, particularly preferably C 2 -C 12 -alkenyl groups. In the context of the present invention alkenyl, which carries two double bonds in arbitrary positions, is also referred to as alkadienyl.
  • alkenyl also includes substituted alkenyl groups which may carry one or more (eg, 1, 2, 3, 4, 5 or more than 5) substituents. Suitable substituents are, for. B. selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, halogen, hydroxy, mercapto (-SH), COOH, carboxylate, SO3H, sulfonate, NE 3 E 4 , nitro and cyano, wherein E 3 and E 4 are independently Hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • substituents are, for. B. selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, halogen, hydroxy, mercapto (-SH), COOH, carboxylate, SO3H, sulfonate, NE 3 E 4 , nitro and cyano, wherein E 3 and E 4 are independently
  • Alkenyl is then, for example, ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl , 3-hexenyl, 4-hexenyl, 5-hexenyl, penta-1,3-dien-1-yl, hexa-1, 4-dien-1-yl, hexa-1, 4-dien-3-yl, hexa -1, 4-dien-6-yl, hexa-1, 5-dien-1-yl, hexa-1, 5-dien-3-yl, hexa-1, 5-dien-4-yl, hepta-1 , 4-dien-1-yl, hepta-1, 4-dien-3-yl, hepta-1, 4-dien-6-yl, hepta-1
  • alkynyl includes unsubstituted or substituted alkynyl groups having one or more non-adjacent triple bonds, such as ethynyl,
  • alkynyl 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4- Hexynyl, 5-hexynyl, and the like.
  • the remarks on alkynyl also apply to the alkynyl groups in alkynyloxy, alkynylthio, etc.
  • Substituted alkynyls preferably carry one or more (eg 1, 2, 3, 4, 5 or more than 5) of the substituents previously mentioned for alkyl.
  • cycloalkyl in the context of the present invention comprises unsubstituted as well as substituted cycloalkyl groups, preferably Cs-Cs-cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, in particular particular Cs-Cs-cycloalkyl.
  • Substituted cycloalkyl groups may have one or more (eg 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably selected independently of one another from alkyl and the substituents mentioned above for the alkyl groups.
  • the cycloalkyl groups preferably carry one or more, for example one, two, three, four or five
  • cycloalkyl groups are 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 4-butylcyclohexyl, 3- and 4-sec-butylcyclohexyl, 3- and 4-tert-butylcyclohexyl, cycloheptyl, 2-, 3- and 4-methylcycloheptyl, 2 , 3- and 4-ethylcycloheptyl, 3- and 4-propylcycloheptyl, 3- and 4-isopropylcycloheptyl, 3- and 4-butylcycloheptyl, 3- and 4-sec-butylcycloheptyl, 3- and 4-tert-butylcycloo
  • cycloalkenyl includes unsubstituted and substituted monounsaturated hydrocarbon groups having 3 to 8, preferably 5 to 6 carbon ring members, such as cyclopenten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl, cyclohexene 4-yl and the like. Suitable substituents are those previously mentioned for cycloalkyl.
  • bicycloalkyl preferably includes bicyclic hydrocarbon radicals having 5 to 10 C atoms, such as bicyclo [2.2.1] hept-1-yl, bicyclo [2.2.1] hept-2-yl, bicyclo [2.2.1] hept-7-yl , Bicyclo [2.2.2] oct-1-yl, bicyclo [2.2.2] oct-2-yl, bicyclo [3.3.0] octyl, bicyclo [4.4.0] decyl and the like.
  • aryl in the context of the present invention comprises mononuclear or polynuclear aromatic hydrocarbon radicals which may be unsubstituted or substituted.
  • Aryl is preferably unsubstituted. Or substituted phenyl,
  • aryl may have one or more (eg 1, 2, 3, 4, 5 or more than 5) substituents depending on the number and size of their ring systems.
  • E 5 and E 6 are independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • Halogen substituents are preferably fluorine, chlorine or bromine.
  • Aryl is particularly preferably Phenyl, which in the case of a substitution generally 1, 2, 3, 4 or 5, preferably 1, 2 or 3 substituents can carry.
  • Aryl which carries one or more radicals is, for example, 2-, 3- and 4-methylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethylphenyl, 2,4,6-trimethylphenyl , 2-, 3- and 4-ethylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dipropylphenyl, 2,4,6-tripropylphenyl, 2-, 3- and 4-isopropylphenyl, 2,4-, 2,5-, 3 , 5- and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dibutylphenyl , 2,4,6-Tributylphenyl
  • 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 are substituted by heteroatoms selected from oxygen, Nitrogen, sulfur and a group -NR e - are replaced and which is unsubstituted or substituted by 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, tetrahydropyranyl, 1, 2-oxazolin-5-yl, 1, 3-oxazolin-2-yl and dioxanyl.
  • heteroaryl in the context of the present invention comprises unsubstituted or substituted, heteroaromatic, mono- or polynuclear groups, 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 preferably selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, hydroxy, carboxy, halogen and cyano.
  • Nitrogen-containing 5- to 7-membered heterocycloalkyl or heteroaryl radicals which optionally contain further heteroatoms selected from oxygen and sulfur include, for example, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, 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-dodecylaminosulfonyl, N, N-diphenylaminosulfonyl, and N, N-bis (4-chlorophenyl) aminosulfonyl;
  • 2-dioxanyl 1-morpholinyl, 1-thiomorpholinyl, 2- and 3-tetrahydrofuryl, 1-, 2- and 3-pyrrolidinyl, 1-piperazyl, 1-diketopiperazyl and 1-, 2-, 3- and 4-piperidyl;
  • Preferred fluorine-containing radicals R a and R b are the following:
  • 2,6-Dibromo-4- (trifluoromethyl) phenyl 4-trifluoromethyl-2,3,5,6-tetrafluorophenyl, 3-fluoro-4-trifluoromethylphenyl, 2,5-difluoro-4-trifluoromethylphenyl, 3,5-difluoro 4-trifluoromethylphenyl, 2,3-difluoro-4-trifluoromethylphenyl, 2,4-bis (trifluoromethyl) phenyl, 3-chloro-4-trifluoromethylphenyl, 2-bromo-4,5-di (trifluoromethyl) phenyl, 5-chloro 2-nitro-4- (trifluoromethyl) phenyl, 2,4,6-tris (trifluoromethyl) phenyl, 3,4-bis (trifluoromethyl) phenyl, 2-fluoro-3-trifluoromethylphenyl, 2-iodo-4-trifluoromethylphenyl, 2-nitro-4,5
  • 3-fluorophenethyl 4-trifluoromethylphenethyl, 2,3-difluorophenethyl, 3,4-difluorophenethyl, 2,4-difluorophenethyl, 2,5-difluorophenethyl, 3,5-difluorophenethyl, 2,6-difluorophenethyl, 4- (4-fluorophenyl ) phenethyl, 3,5-di (trifluoromethyl) phenethyl, pentafluorophenethyl, 2,4-di (trifluoromethyl) phenethyl, 2-nitro-4- (trifluoromethyl) phenethyl, (2-fluoro-3-trifluoromethyl) phenethyl, (2- Fluoro-5-trifluoromethyl) phenethyl, (3-fluoro-5-trifluoromethyl) phenethyl, (4-fluoro
  • a further embodiment of the invention relates to compounds of the formula (I), where the groups R a and R b are groups of the formula (A) (so-called dovetail radicals).
  • the radicals R e are selected from C 4 -Ce-Al kyl, preferably Cs-Cz-alkyl.
  • the groups R a and R b then both represent a group of the formula
  • radicals R e are selected from C 4 -Ce-Al kyl, preferably Cs-Cz-alkyl. At the leftovers
  • R e are then in particular linear alkyl radicals which are not interrupted by oxygen atoms.
  • a preferred example of a group of formula (A) is
  • R n1 , R n2 , R n3 and R n4 are bromine.
  • Rylenetetracarboxylic dianhydrides are referred to below as compounds I.A.
  • Rylenetetracarboxylic diimides are referred to below as compounds I.B, where compounds I. Ba
  • radicals R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 are halogen or cyano, especially bromine, where at least one of the radicals R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 or R 24 is bromine and R a and R b independently of one another have one of the abovementioned meanings.
  • At least one of R a or R b is an electron-withdrawing substituted radical.
  • At least one of the radicals R a and R b is a radical mono- or polysubstituted with fluorine. Particularly preferably, both R a and R b are a radical mono- or polysubstituted with fluorine.
  • suitable fluorinated radicals Reference will also be made to the statements made at the outset.
  • radicals R a and R b are the same.
  • a further preferred embodiment is compounds of the general formulas I.Bbi and I.Bb2 where n and R n1 , R n2 , R n3 and R n4 have the meanings given above and X see for a divalent bridging group having 2 to 5 atoms between the flanking bonds stands.
  • the bridging groups X are selected from groups of the formulas (III.a) to (III.d)
  • R ⁇ v , R v , R v ⁇ , R v “, R v ⁇ " and R ⁇ x independently of one another are hydrogen, alkyl, alkoxy, cycloalkyl, cycloalkoxy, heterocycloalkyl, heterocycloalkoxy, aryl, aryloxy, hetaryl, hetaryloxy, halogen, hydroxyl, mercapto ( -SH), COOH, carboxylate, SO 3 H, sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 , nitro, alkoxycarbonyl, acyl or cyano, where E 1 and E 2 are each independently hydrogen, alkyl, cycloalkyl, Heterocycloalkyl, aryl or hetaryl are available.
  • the compounds of the general formula I according to the invention can be prepared starting from known compounds having the same skeletal skeleton and carrying at least one hydrogen atom as radicals R n1 , R n2 , R n3 and R n4 .
  • Another object of the present invention relates to processes for the preparation of compounds of formula I,
  • n, R n1 , R n2 , R n3 , R n4 , Y 1 , Y 2 , Z 1 , Z 2 , Z 3 and Z 4 have one of the meanings given above,
  • R n1 , R n2 , R n3 or R n4 is hydrogen
  • the remaining radicals R n1 , R n2 , R n3 and R n4 are halogen or cyano and especially bromine and n
  • Y 1 , Y 2 , Z 1 , Z 2 , Z 3 and Z 4 have one of the previously given meaning of a bromination with N, N'-dibromoisocyanuric acid.
  • N, N'-dibromoisocyanuric acid is preferably used in an amount of about 0.8: 1 to 4: 1, more preferably about 0.9: 1 to 2: 1, based on one mole of the radicals R n1 contained in the compounds of formula II , R n2 , R n3 and R n4 , which are hydrogen.
  • the bromination is preferably carried out in the presence of oleum.
  • oleum will be used as a solvent for the bromination reaction.
  • the oleum used for the bromination is preferably at least 20%, more preferably at least 25% and most preferably at least 28%, such as. B. 30% oleum.
  • bromination with N, N'-dibromoisocyanuric acid may also be carried out in the presence of an inorganic or organic acid other than oleum.
  • organic acids such as acetic acid, propionic acid or butyric acid, in particular acetic acid.
  • the organic acid is used as a solvent.
  • the reaction temperature is usually in the range of -10 to 120 ° C.
  • the upper limit of the reaction temperature is usually determined by the boiling point of the solvent or the organic or inorganic acid used.
  • the products may be advantageous to subject the products to further purification.
  • these include, for example, column chromatographic methods, wherein the products z. B. dissolved in a halogenated carbon hydrogen such as methylene chloride or a toluene / or petroleum ether / ethyl acetate mixture, a separation or filtration are subjected to silica gel.
  • a purification by sublimation or crystallization is possible.
  • R n1 , R n2 , R n3 and R n4 are halogen or cyano, especially bromine, in which a rylenetetracarboxylic dianhydride of the formula ILA,
  • R n1 , R n2 , R n3 or R n4 is hydrogen, the remaining radicals R n1 , R n2 , R n3 and R n4 are halogen or cyano, especially bromine, and n is 2, 3 or 4, subjected to bromination with N, N'-dibromoisocyanuric acid.
  • Suitable process conditions for the bromination of the rylene dianhydride are those described above, to which reference is hereby made.
  • the rylenetetracarboximides of the formulas I.Ba, I.Bbi and I.Bb2 are likewise known from the bromination of the corresponding rylenetetracarboximides, in which at least one of R n1 , R n2 , R n3 or R n4 is hydrogen
  • N, N'-dibromoisocyanuric acid can be produced. Usually, however, they will be based on the known rylenetetracarboxylic dianhydrides of the formula ILA for their preparation.
  • a further subject of the present invention relates to processes for the preparation of compounds of the formula I. Ba,
  • R n1 , R n2 , R n3 , R n4 , R a and R b have one of the meanings given above , wherein
  • R n1 , R n2 , R n3 or R n4 is hydrogen, the remaining radicals R n1 , R n2 , R n3 and R n4 are halogen or cyano, especially bromine, and n is 2, 3 or 4 is subjected to bromination with N, N'-dibromoisocyanuric acid, and
  • step b1) the compound obtained in step a1) of a reaction with an amine of
  • the compounds of formula I.Ba can be prepared by a process wherein
  • step b2) subjecting the compound obtained in step a2) to bromination with N, N'-dibromoisocyanuric acid. getting produced.
  • a further subject of the present invention relates to a process for the preparation of compounds of the formulas I.Bbi and / or I.Bb2,
  • n, R n1 , R n2 , R n3 , R n4 and X have one of the meanings given above , in which one
  • R n1 , R n2 , R n3 or R n4 is hydrogen, the remaining radicals R n1 , R n2 , R n3 and R n4 are halogen or cyano, especially bromine, and n is 2, 3 or 4 is subjected to bromination with N, N'-dibromoisocyanuric acid, and
  • step b3) subjecting the compound obtained in step a3) to a reaction with an amine of the formula H 2 NX-NH 2 .
  • the compounds of formulas I.Bbi and / or I.Bb2 can be prepared by a process in which
  • step a4) subjecting a rylene dianhydride of the formula ILA to a reaction with an amine of the formula H 2 NX-NH 2 , and b4) subjecting the compound obtained in step a4) to bromination with N, N'-dibromocyanuric acid.
  • Suitable process conditions for the bromination of the rylene skeleton in steps a1), b2), a3) and b4) are those described above, to which reference is hereby made.
  • the imidation of the carboxylic anhydride groups in the reaction steps b1), a2), b3) and a4) is known in principle and z. B. in DE 10 2004 007 382 A1.
  • the reaction of the dianhydride with the primary amine is carried out in the presence of an aromatic solvent such as toluene, xylene, mesitylene, phenol or a polar aprotic solvent.
  • aromatic solvent such as toluene, xylene, mesitylene, phenol or a polar aprotic solvent.
  • Suitable polar aprotic solvents are nitrogen heterocycles, such as pyridine, pyrimidine, quinoline, isoquinoline, quinaldine, N-methylpiperidine, N-methylpiperidone and N-methylpyrrolidone.
  • the reaction can be carried out in the presence of an imidation catalyst.
  • Suitable imidation catalysts are organic and inorganic acids, eg. For example, formic acid, acetic acid, propionic acid and phosphoric acid.
  • Suitable imidation catalysts are also organic and inorganic salts of transition metals, such as zinc, iron, copper and magnesium. These include z. As zinc acetate, zinc propionate, zinc oxide, iron (II) acetate, iron (III) chloride, iron (II) sulfate, copper (II) acetate, copper (II) oxide and magnesium acetate.
  • an imidation catalyst is preferably carried out in the reaction of aromatic amines and is generally also advantageous for the reaction of cycloaliphatic amines.
  • the use of an imidation catalyst can generally be dispensed with.
  • the amount used of the imidation catalyst is preferably 5 to 80 wt .-%, particularly preferably 10 to 75 wt .-%, based on the total weight of the compound to be amidated.
  • the molar ratio of amine to dianhydride is about 2: 1 to 10: 1, more preferably 2: 1 to 4: 1, e.g. From 2.2: 1 to 3: 1.
  • organic acids previously mentioned as imidation catalysts are also suitable as solvents.
  • the reaction temperature is in the steps b1), a2), b3) or a4) is generally ambient temperature to 200 0 C, preferably 40 to 160 0 C.
  • the reaction of aliphatic and cycloaliphatic amines is preferably carried out in a temperature range of about 60 0 C to 100 0 C.
  • the reaction of aromatic amines is preferably carried out in a temperature range of about 120 to 160 0 C.
  • the reaction in the reaction steps b1), a2), b3) or a4) under a protective gas atmosphere, such. Nitrogen.
  • reaction steps b1), a2), b3) or a4) can be carried out under atmospheric pressure or, if desired, under elevated pressure.
  • a suitable pressure range is in the range of about 0.8 to 10 bar.
  • the use is under increased pressure.
  • the water formed in the reaction in steps b1), a2), b3) or a4) can be separated by distillation by methods known to the person skilled in the art.
  • the diimides obtained in reaction step b1), a2), b3) or a4) can be used without further purification.
  • the products for use of the products as semiconductors, however, it may be advantageous to subject the products to further purification.
  • These include, for example, column chromatographic methods, wherein the products are preferably dissolved in a halogenated hydrocarbon, such as methylene chloride, subjected to separation or filtration on silica gel.
  • the compounds of the formula I are particularly advantageous as organic semiconductors. They usually act as n-semiconductors. If the compounds of the formula I used according to the invention are combined with other semiconductors and if it results from the position of the energy levels that the other semiconductors function as n-semiconductors, the compounds I can also function as p-type semiconductors by way of exception.
  • the compounds of the formula I are distinguished by their air stability. Furthermore, they have a high charge transport mobility, which clearly knew about organic semiconductor materials. They also have a high on / off ratio.
  • the compounds of the formula I are suitable in a particularly advantageous manner for organic field effect transistors. They can be used, for example, for the production of integrated circuits (ICs), for which hitherto usual n-channel MOSFET (metal oxide semiconductor field-effect transistor) are used. These are then CMOS analog semiconductor devices, eg. For microprocessors, microcontrollers, static RAM, and other digital logic cireuits.
  • CMOS analog semiconductor devices eg.
  • the compounds of the formula I can be further processed by one of the following methods: printing (offset, flexo, gravure, screen, inkjet, electrophotography), evaporation, laser transfer, photolithography, drop casting. They are particularly suitable for use in displays (especially large and / or flexible displays) and RFI D tags.
  • the compounds of the formula I are particularly advantageous as electron conductors in organic field effect transistors, organic solar cells and in organic light emitting diodes. They are furthermore particularly advantageous as exciton-transport material in excitonic solar cells.
  • the compounds of the formula I 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.
  • z. 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. From W.A. Crossland, I.D. Sprigle and A.B.
  • the compounds of formula I are also particularly suitable for laser welding or thermal management.
  • 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 a semiconductor, especially as an n-type semiconductor.
  • the invention further substrates with a plurality of organic field effect transistors, wherein at least a portion of the Feldcouransistoren at least one compound of formula I, as defined above, contains 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.
  • 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 forming part of an integrated circuit, and wherein at least a portion of the transistors comprise 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, ceramics, SiO 2, especially quartz), 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 may be flexible or inflexible, 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, optional
  • Suitable dielectrics are SiO 2, polystyrene, poly- ⁇ -methylstyrene, polyolefins (such as polypropylene, polyethylene, polyisobutene) polyvinylcarbazole, fluorinated polymers (eg Cytop), cyanopulluans (eg CYMM), polyvinylphenol, poly-p xylene, polyvinyl chloride, or thermally or moisture crosslinkable polymers.
  • Special dielectrics are "seif assembled nanodielectrics", ie polymers derived from SiCI functionalities containing monomers such.
  • Dilution can be crosslinked with solvents (see, for example, Faccietti Adv. Mat. 2005, 17, 1705-1725).
  • solvents see, for example, Faccietti Adv. Mat. 2005, 17, 1705-1725.
  • hydroxyl-containing polymers such as polyvinylphenol or polyvinyl alcohol or copolymers of vinylphenol and styrene can serve as crosslinking components.
  • 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 , Si 3 N 4 , etc., ferroelectric insulators such as AbO 3 , Ta 2 Os, La 2 Os, TiO 2 , Y 2 O 3 , etc., organic insulators such as polyimides, benzocyclobutene (BCB), polyvinyl alcohols, polyacrylates, etc., and combinations thereof.
  • inorganic insulators such as SiO 2 , Si 3 N 4 , etc.
  • ferroelectric insulators such as AbO 3 , Ta 2 Os, La 2 Os, TiO 2 , Y 2 O 3 , etc.
  • organic insulators such as polyimides, benzocyclobutene (BCB), polyvinyl alcohols, polyacrylates, etc., and combinations thereof.
  • Preferred electrically conductive materials have a resistivity of less than 10 " 3 , preferably less than 10 " 4 , especially less than 10 "6 or 10 " 7 ohms x meters.
  • drain and source electrodes are at least partially on the organic semiconductor material.
  • the substrate may include other components commonly used in semiconductor materials or ICs, such as insulators, resistors, capacitors, printed conductors, 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 the general formula I is carried out 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.
  • 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 during the deposition is preferably in a range from about 20 to 250 ° C., particularly preferably 50 to 200 ° C.
  • 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 the 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.
  • the deposition of at least one compound of general formula I (and optionally other semiconductor materials) by a spin coating can therefore also be used in a wet processing method (wet processing) for the production of semiconductor substrates.
  • the compounds of the formula I should therefore also be suitable for the production of semiconductor elements, especially OFETs or based on OFETs, by a printing process. Standard printing processes (inkjet, flexo, offset, engraving, rotogravure, nano print) can be used.
  • 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 to these "semiconductor inks" thickening substances, such as polymers, for. 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 located on the substrate, a gate insulating layer located thereon and the substrate, a semiconductor layer located 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 prior to the separation of at least one compound of general formula I (and optionally at least one further semiconductor material) is subjected to 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 preferred with at least one compound (C1) which is suitable for binding to the surface of the substrate and to 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 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. In US Pat. No. 11 / 353,934, which is hereby incorporated 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 bonding, coordinative interaction, van der Waals interactions, eg. Dipole-dipole interactions) etc. and combinations thereof.
  • Suitable compounds of the general formula (C1) are:
  • alkyltrialkoxysilanes such as n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltri- (n-propyl) oxysilane, n-octadecyltri- (isopropyl) oxysilane;
  • Trialkoxyaminoalkylsilanes such as triethoxyaminopropylsilane and N [(3-triethoxysilyl) -propyl] -ethylenediamine;
  • Trialkoxyalkyl-3-glycidyl ether silanes such as triethoxypropyl
  • Trialkoxyallylsilanes such as allyltrimethoxysilane; Trialkoxy (isocyanatoalkyl) silanes; Trialkoxysilyl (meth) acryloxyalkanes and trialkoxysilyl (meth) acrylamidoalkanes such as 1-triethoxysilyl-3-acryloxypropane.
  • Amines, phosphines and sulfur containing compounds especially thiols.
  • the compound (C1) is selected from alkyltrialkoxysilanes, especially n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane; Hexaalkyldisilazanes, and especially hexamethyldisilazane (HMDS); Cs-Cso-alkylthiols, especially hexadecanethiol; Mercaptocarboxylic acids and mercaptosulphonic acids, especially mercaptoacetic acid,
  • Top Contact Top Gate
  • Bottom Contact Bottom Gate
  • B. a VOFET Very organic field effect transistor
  • 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 components biological and chemical detectors or sensors
  • 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. B. (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.
  • the compounds of the formula I are used as organic n-semiconductors in an inverter.
  • the compounds of the formula I are furthermore particularly advantageous for use in organic photovoltaics (OPV).
  • OOV organic photovoltaics
  • these compounds are suitable for use in dye-sensitized solar cells.
  • 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).
  • Such solar cells are referred to as excitonic solar cells within the meaning of the invention.
  • the direct conversion of solar energy into electrical energy in solar cells is based on the internal photoelectric effect of a semiconductor material, ie the generation of electron-hole pairs by absorption of photons and the separation of the negative and positive charge carriers at a pn 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 pn 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.
  • 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. As described in US 2005/0098726 A1 and US 2005/0224905 A1, which is incorporated herein by reference in its entirety.
  • Suitable substrates are for.
  • oxidic materials such as glass, ceramic, SiÜ2, especially quartz, etc.
  • polymers eg., Polyvinyl chloride, polyolefins, such as polyethylene and polypropylene, polyesters, fluoropolymers, polyamides, polyurethanes, polyalkyl (meth) - acrylates, polystyrene and mixtures and composites thereof
  • combinations thereof eg., Polyvinyl chloride, polyolefins, such as polyethylene and polypropylene, polyesters, fluoropolymers, polyamides, polyurethanes, polyalkyl (meth) - acrylates, polystyrene and mixtures and composites thereof.
  • metals preferably groups 2, 8, 9, 10, 11 or 13 of the Periodic Table, eg Pt, Au, Ag, Cu, Al, In, Mg, Ca
  • electrodes cathode, anode.
  • 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
  • an essentially transparent material is used as the anode with respect to incident light. This includes z.
  • 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 at least one layer containing as organic semiconductor material at least one compound selected from compounds of the formula I 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, exciton blocking layers, EBL) that are not supposed to absorb multiplication layers. Suitable excitons and holes blocking layers are for. As described in US 6,451, 415.
  • Suitable Excitonenblocker für z. B. Bathocuproine (BCP), 4,4 ', 4 "-Tris [3-methylphenyl (phenyl) amino] triphenylamine (m-MTDATA) or Polyethylendioxythiophen (PEDOT), as described in US 7,026,041.
  • BCP Bathocuproine
  • m-MTDATA 4,4 ', 4 "-Tris [3-methylphenyl (phenyl) amino] triphenylamine
  • PEDOT Polyethylendioxythiophen
  • 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 (hole transport material, hole transport material), the corresponding ETM (exciton transport material, exciton transport material) must be selected such that, after excitation of the compounds, rapid electron transfer to the ETM occurs. Suitable ETMs are z. B. C60 and other fullerenes, perylene-3,4: 9,10-bis (dicarboximide) (PTCDI), etc. If at least one compound of formula I is used as ETM, the complementary HTM must be chosen so that after excitation of the Connecting a fast 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., 252, 243-258 (1994).) Or as a bulk heterojunction or interpenetrated donor-acceptor network, cf., for example, Messner, M. Möbus, F. Stölzle, Mol. BCJ Brabec, NS Sariciftci, JC Hummelen, Adv. Funct. Mater., 11 (1), 15 (2001).).
  • Thin layers of the compounds and of all other layers can be obtained by vacuum evaporation or in an 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, engraving, 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 and substituted acenes.
  • Substituted acetals include 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. These include 2,9-dialkylpentacenes and 2,10-dialkylpentacenes, 2,10-dialkoxypentacenes, 1, 4,8,1-tetraalkoxypentacenes and rubrene (5,6,11,12-tetraphenylnaphthacene). Suitable substituted pentacenes are described in US 2003/0100779 and US Pat. No. 6,864,396.
  • a preferred acene is rubrene (5,6,1 1, 12-tetraphenylnaphthacene).
  • Phthalocyanines such as hexadecachlorophthalocyanines and hexadecafluorophthalocyanines, containing metal-free and divalent metals, in particular those of titanyloxy, vanadyloxy, iron, copper, zinc, in particular copper phthalocyanine, zinc phthalocyanine cyanine and metal-free phthalocyanine, hexadecachloro copper phthalocyanine, hexadecachlorozinc phthalocyanine, metal-free hexadechlorophthacocyanine, hexadecafluoro copper phthalocyanine, hexadecafluorophthalocyanine or metal-free hexafluorophathocyanocyanine.
  • metal-free and divalent metals in particular those of titanyloxy, vanadyloxy, iron, copper, zinc, in particular copper phthalocyanine, zinc phthalocyanine cyanine and metal-free phthalocyanine,
  • Porphyrins such as. 5,10,15,20-tetra (3-pyridyl) porphyrin (TpyP).
  • Liquid crystalline (LC) materials such as. Hexabenzocoronene (HBC-PhCl 2) or other coronene, coronodiimides, or triphenylenes such as 2,3,6,7,10,1-hexahexylthiotriphenylene (HTT6) or 2,3,6,7,10,11-hexakis - (4-n-nonylphenyl) -triphenylene (PTP9), 2,3,6,7,10,11-hexakis- (undecyloxy) -triphenylenes (HAT11).
  • HBC-PhCl 2 Hexabenzocoronene
  • HTT6 2,3,6,7,10,1-hexahexylthiotriphenylene
  • PTP9 2,3,6,7,10,11-hexakis- (undecyloxy) -triphenylenes
  • Particularly preferred are LCs 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 ⁇ , ⁇ -di (C 1 -C 8) -alkyloligothiophenes
  • Preferred thiophenes, oligothiophenes and substituted derivatives thereof are poly-3-hexylthiophene (P3HT) or compounds of the type ⁇ , ⁇ '-bis (2,2-dicyanovinyl) quinethiophene (DCV5T), poly (3- (4-octylphenyl) - 2,2'-bithiophene) (PTOPT), poly (3- (4 '- (1 ", 4", 7 "-trioxaoctyl) phenyl) thiophene) (PEOPT), (poly (3- (2'-methoxy-) 5'-octylphenyl) -thiophene)) (POMeOPT), poly (3-octylthiophene) (P3OT), pyridine-containing polymers such as poly (pyridopyrazine vinylene), poly (pyridopyrazine vinylene) modified with alkyl groups, e
  • PCPDTBT Poly [2,6- (4,4-bis (2-ethylhexyl) -4 H -cyclopenta [2,1-b; 3,4 -b '] - dithiophene) -4,7- (2,1,3-benzothiadiazole).
  • Paraphenylenevinylene and paraphenylenevinylene containing oligomers or polymers such.
  • PPE-PPV hybrid polymers phenylene-ethynylene / phenylene-vinylene hybrid polymers).
  • Polyfluorene and alternating polyfluorene copolymers such. With 4,7-dithien-2'-yl-2,1,3-benzothiadiazole, and further poly (9,9'-dioctylfluorene-co-benzothiadiazole) (F 8 BT), poly (9,9'- dioctylfluorene-co-bis-N, N '- (4-butylphenyl) -bis-N, N'-phenyl-1, 4-phenylenediamine) (PFB).
  • Polycarbazoles d. H. Carbazole containing oligomers and polymers such as (2,7) and (3,6).
  • Triarylamines polytriarylamines, polycyclopentadienes, polypyrroles, polyfuran, polysilanes, polyphospholes, N, N'-bis (3-methylphenyl) -N, N'-bis (phenyl) benzidine (TPD), 4,4'-bis ( carbazol-9-yl) biphenyl (CBP), 2,2 ', 7,7'-tetrakis (N, N-di-p-methoxyphenylamine) - 9,9'-spirobifluorene (spiro-MeOTAD).
  • PCBM [6,6] -phenyl-C6i-butyric acid methyl ester
  • p-n mixed materials d. H. Donor and acceptor in one material, polymer, block polymers, polymers with C60s, C60 azo dyes, trimeric mixed material containing carotenoid type compounds, porphyrin type and quinoidal liquid crystalline compounds as donor / acceptor systems, as described by Kelly in S. Adv. Mater. 2006, 18, 1754.
  • All of the aforementioned semiconductor materials may also be doped.
  • dopants Br 2, tetrafluorotetracyanoquinodimethane (F 4 -TCNQ), etc.
  • OLED organic light-emitting diode
  • the compounds of the formula I can serve as charge transport material (electron conductor).
  • Organic light emitting diodes are basically made up of several layers. These include: 1. anode 2. hole-transporting layer 3. light-emitting layer 4. electron-transporting layer 5. cathode. It is also possible that the organi- see light-emitting diode does not have all of the layers mentioned, for example, an organic light-emitting diode with the layers (1) (anode), (3) (light-emitting layer) and (5) (cathode) is also suitable, the functions of the layers ( 2) (hole-transporting layer) and (4) (electron-transporting layer) are taken over by the adjacent layers. OLEDs comprising layers (1), (2), (3) and (5) or layers (1), (3), (4) and (5) are also suitable.
  • OLEDs organic light-emitting diodes and methods for their preparation are known in principle to those skilled in the art, for example from WO 2005/019373. Suitable materials for the individual layers of OLEDs are z. As disclosed in WO 00/70655. The disclosure of these documents is hereby incorporated by reference.
  • the production of OLEDs according to the invention can be carried out by methods known to the person skilled in the art. Generally, an OLED is made by sequential vapor deposition of the individual layers onto a suitable substrate. Suitable substrates are, for example, glass or polymer films. For vapor deposition, conventional techniques can be used such as thermal evaporation, chemical vapor deposition and others.
  • the organic layers may be coated from solutions or dispersions in suitable solvents using coating techniques known to those skilled in the art.
  • Compositions which, in addition to a compound of the general formula I, comprise a polymeric material in one of the layers of the OLEDs, preferably in the light-emitting layer, are generally applied as a layer by processing from solution.
  • OLEDs can be obtained with high efficiency.
  • the OLEDs according to the invention can be used in all devices in which electroluminescence is useful. Suitable devices are preferably selected from stationary and mobile screens. Stationary screens are z. For example, screens of computers, televisions, screens in printers, kitchen appliances, and billboards, lights, and billboards. Mobile screens are z. For example, screens in cell phones, laptops, digital cameras, vehicles, and destination displays on buses and trains.
  • the compounds I can be used in OLEDs with inverse structure. The compounds I are preferably used in these inverse OLEDs again in the light-emitting layer. The construction of inverse OLEDs and the materials usually used therein are known to the person skilled in the art.
  • Suitable purification methods include transferring the compounds gene of formula I in the gas phase. These include cleaning by sublimation or PVD (physical vapor deposition). Preference is given to a fractional sublimation. For fractional sublimation and / or deposition of the compound, a temperature gradient is used. Preferably, the compound of the formula I is sublimated with heating in a carrier gas stream. The carrier gas then flows through a separation chamber. A suitable separation chamber has at least two different separation zones with different temperatures. Preferably, a so-called "three-zone furnace” is used. A suitable method and apparatus for fractional sublimation is described in US 4,036,594.
  • Another object of the invention is a method for the deposition or application of at least one compound of formula I on a (em) substrate by a gas phase deposition method or a wet application method.
  • N, N'-dimethyl-perylene-3,4: 9,10-tetracarboxylic acid imide was obtained as a red solid in an amount of 3.4 g (yield 77%).

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne des dérivés d'acide rylène tétracarboxylique substitués par brome de formule générale (I) dans laquelle n vaut 2, 3 ou 4; Rn1, Rn2, Rn3 et Rn4 sont halogène ou cyano, en particulier Br, au moins l'un des radicaux Rn1, Rn2, Rn3 et Rn4 étant Br; Y1 et Y2 sont O ou NRb, où Rb est hydrogène ou un radical organyle; Z1, Z2, Z3 et Z4 sont O. Dans le cas où Y1 est NRa, l'un des radicaux Z1 et Z2 peut également être NRC, les radicaux Ra et Rc formant ensemble une groupe de pontage comprenant de 2 à 5 atomes entre les liaisons adjacentes, et dans le cas où Y2 est NRb, l'un des radicaux Z3 et Z4 peut également être NRd, les radicaux Rb et Rd formant ensemble un groupe de pontage comprenant de 2 à 5 atomes entre les liaisons adjacentes. L'invention concerne également la préparation de ces composés de formule générale I par conversion d'un composé correspondant, au moins l'un des radicaux Rn1, Rn2, Rn3 et/ou Rn 4 étant hydrogène, avec de l'acide N,N'-dibromisocyanurique, et l'utilisation de composés de formule générale I comme substances d'émission, substances de transport de charges ou substance de transport d'excitons.
PCT/EP2008/058011 2007-06-25 2008-06-24 Dérivés d'acide rylène tétracarboxylique substitués par brome et leur utilisation Ceased WO2009000831A1 (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
TWI598349B (zh) * 2011-05-11 2017-09-11 巴地斯顏料化工廠 以鹵化苝為基質之半導體材料

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WO2003104232A1 (fr) * 2002-06-07 2003-12-18 Basf Aktiengesellschaft Diimide d'acide tétracarbonique terrylène 1,6,9,14-tétrasubstitué
WO2006037539A1 (fr) * 2004-10-05 2006-04-13 Basf Aktiengesellschaft Halogenation de rylene-carboximides a halogene elementaire dans un melange a deux phases comprenant un solvant organique et de l'eau, avec prelevement en continu, a partir du solvant organique, de l'hydracide halogene forme
WO2006058674A1 (fr) * 2004-11-29 2006-06-08 Basf Aktiengesellschaft Diimides d'acide tetracarboxylique de rylene substitues par des groupes amino cycliques

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WO2003104232A1 (fr) * 2002-06-07 2003-12-18 Basf Aktiengesellschaft Diimide d'acide tétracarbonique terrylène 1,6,9,14-tétrasubstitué
WO2006037539A1 (fr) * 2004-10-05 2006-04-13 Basf Aktiengesellschaft Halogenation de rylene-carboximides a halogene elementaire dans un melange a deux phases comprenant un solvant organique et de l'eau, avec prelevement en continu, a partir du solvant organique, de l'hydracide halogene forme
WO2006058674A1 (fr) * 2004-11-29 2006-06-08 Basf Aktiengesellschaft Diimides d'acide tetracarboxylique de rylene substitues par des groupes amino cycliques

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TACHIKAWA ET AL: "Hybrid density functional theory (DFT) study on electronic states of halogen-substituted organic-inorganic hybrid compounds: Al-NTCDA", JAPANESE JOURNAL OF APPLIED PHYSICS, JAPAN SOCIETY OF APPLIED PHYSICS, TOKYO.; JP, vol. 44, no. 6A, 1 January 2005 (2005-01-01), pages 3769 - 3773, XP002429103, ISSN: 0021-4922 *

Cited By (2)

* Cited by examiner, † Cited by third party
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
TWI598349B (zh) * 2011-05-11 2017-09-11 巴地斯顏料化工廠 以鹵化苝為基質之半導體材料

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