US20110068328A1 - Halogen-containing perylenetetracarboxylic acid derivatives and the use thereof - Google Patents

Halogen-containing perylenetetracarboxylic acid derivatives and the use thereof Download PDF

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US20110068328A1
US20110068328A1 US12/673,908 US67390808A US2011068328A1 US 20110068328 A1 US20110068328 A1 US 20110068328A1 US 67390808 A US67390808 A US 67390808A US 2011068328 A1 US2011068328 A1 US 2011068328A1
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Martin Koenemann
Gabriele Mattern
Gerd Weber
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Definitions

  • the present invention relates to highly halogenated, especially chlorinated and/or fluorinated, especially perhalogenated, perylenetetracarboxylic acid derivatives and to their use as emitter materials, charge transport materials or exciton transport materials.
  • organic semiconductors have advantages over the classical inorganic semiconductors, for example better substrate compatibility and better processability of the semiconductor components based on them. They allow processing on flexible substrates and enable their interface orbital energies to be adjusted precisely to the particular application sector by the methods of molecular modeling. The significantly reduced costs of such components have brought a renaissance to the field of research of organic electronics. “Organic electronics” is concerned principally with the development of new materials and manufacturing processes for the production of electronic components based on organic semiconductor layers.
  • OLEDs organic field-effect transistors
  • OLEDs organic light-emitting diodes
  • photovoltaics photovoltaics
  • OLEDs organic field-effect transistors
  • OLEDs exploit the property of materials of emitting light when they are excited by electrical current.
  • OLEDs are particularly of interest as alternatives to cathode ray tubes and liquid-crystal displays for producing flat visual display units. Owing to the very compact design and the intrinsically lower power consumption, devices which comprise OLEDs are suitable especially for mobile applications, for example for applications in cellphones, laptops, etc.
  • R n1 , R n2 , R n3 and R n4 radicals is fluorine, optionally at least one further R n1 , R n2 , R n3 and R n4 radical is a substituent which is selected independently from Cl and Br, and the remaining radicals are each 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 each O, where, in the case that Y 1 is NR a , one of the Z 1 and Z 2 radicals may also be NR c , where the R a and R c radicals together are a bridging group having from 2 to 5 atoms between the flanking bonds, and where, in the case that Y 2 is NR b , one of the Z 3 and Z 4 radicals may also be NR
  • the present invention therefore relates firstly to compounds of the general formula (I)
  • 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 each O or S and the R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals are each chlorine and/or fluorine, where 1 or 2 of the R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals may also be CN and/or 1 R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radical may be hydrogen, and where, in the case that Y 1 is NR a , one of the Z 1 and Z 2 radicals may also be NR c , where the R a and R c radicals together are a bridging X group having from 2 to 5 atoms
  • the invention therefore further relates to the use of the compounds of the formula (I) as emitter materials, charge transport materials or exciton transport materials.
  • alkyl comprises straight-chain or branched alkyl. It is preferably straight-chain or branched C 1 -C 30 -alkyl, especially C 1 -C 20 -alkyl and most preferably C 1 -C 12 -alkyl.
  • alkyl groups are especially 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.
  • alkyl also comprises alkyl radicals whose carbon chains may be interrupted by one or more nonadjacent groups which are selected from —O—, —S—, —NR f —, —C( ⁇ O)—, —S( ⁇ O)— and/or —S( ⁇ O) 2 —.
  • R f is preferably hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • the expression alkyl also comprises substituted alkyl radicals. Substituted alkyl groups may, depending on the length of the alkyl chain, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents.
  • Halogen substituents are preferably fluorine, chlorine or bromine.
  • Carboxylate and sulfonate are, respectively, a derivative of a carboxylic acid function or a sulfonic acid function, especially a metal carboxylate or sulfonate, a carboxylic ester or sulfonic ester function or a carboxamide or sulfonamide function.
  • Cycloalkyl, heterocycloalkyl, aryl and hetaryl substituents of the alkyl groups may in turn be unsubstituted or substituted; suitable substituents are those specified below for these groups.
  • alkyl also apply to the alkyl moieties in alkoxy, alkyl-amino, alkylthio, alkylsulfynyl, alkylsulfonyl, etc.
  • Aryl-substituted alkyl radicals (“arylalkyl”) have at least one unsubstituted or substituted aryl group as defined below.
  • the alkyl group in “arylalkyl” may bear at least one further substituent and/or be interrupted by one or more nonadjacent groups which are selected from —O—, —S—, —NR f —, —CO— and/or —SO 2 —.
  • R f is as defined above.
  • Arylalkyl is preferably phenyl-C 1 -C 10 -alkyl, more preferably phenyl-C 1 -C 4 -alkyl, for example 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, 1-(phenmethyl)-1-(methyl)eth-1-yl or (phenmethyl)-1-(methyl)prop-1-yl; preferably benzyl and 2-phenethyl.
  • alkenyl comprises straight-chain and branched alkenyl groups which, depending on the chain length, may bear one or more double bonds (e.g. 1, 2, 3, 4 or more than 4). Preference is given to C 2 -C 18 -, particular preference to C 2 -C 12 -alkenyl groups. Straight-chain or branched alkenyl groups having two double bonds are also referred to hereinafter as alkadienyl.
  • alkenyl also comprises substituted alkenyl groups which may bear one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents.
  • Suitable substituents are, for example, selected from cycloalkyl, heterocycloalkyl, aryl, hetaryl, halogen, hydroxyl, mercapto, COOH, carboxylate, SO 3 H, sulfonate, NE 3 E 4 , nitro and cyano, where E 3 and E 4 are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • 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-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, h
  • alkynyl comprises unsubstituted or substituted alkynyl groups which have one or more nonadjacent triple bonds, such as ethynyl, 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.
  • alkynyl also apply to the alkynyl groups in alkynyloxy, alkynylthio, etc.
  • Substituted alkynyls preferably bear one or more (e.g. 1, 2, 3, 4, 5 or more than 5) of the substituents specified above for alkyl.
  • cycloalkyl comprises unsubstituted or else substituted cycloalkyl groups, preferably C 3 -C 8 -cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, especially C 5 -C 8 -cycloalkyl.
  • Substituted cycloalkyl groups may have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents. These are preferably each independently selected from alkyl and the substituents specified above for the alkyl groups.
  • the cycloalkyl groups preferably bear one or more, for example one, two, three, four or five, C 1 -C 6 -alkyl groups.
  • 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-butylcyclohyl
  • cycloalkenyl comprises unsubstituted and substituted monounsaturated hydrocarbon groups having from 3 to 8, preferably from 5 to 6 carbon ring members, such as cyclopenten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl, cyclohexen-4-yl and the like. Suitable substituents are those specified above for cycloalkyl.
  • bicycloalkyl preferably comprises bicyclic hydrocarbon radicals having from 5 to 10 carbon 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 comprises mono- or polycyclic aromatic hydrocarbon radicals which may be unsubstituted or substituted.
  • Aryl is preferably unsubstituted or substituted phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, etc., and more preferably phenyl or naphthyl.
  • Substituted aryls may, depending on the number and size of their ring systems, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5) substituents.
  • E 5 and E 6 are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • Halogen substituents are preferably fluorine, chlorine or bromine.
  • Aryl is more preferably phenyl which, in the case of substitution, may bear generally 1, 2, 3, 4 or 5, preferably 1, 2 or 3 substituents. These are preferably each independently selected from alkyl and the substituents mentioned above for the alkyl groups.
  • Aryl which bears 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-ethyl-phenyl, 2,4-, 2,5-, 3,5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propyl-phenyl, 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, 2-
  • heterocycloalkyl comprises nonaromatic, unsaturated or fully saturated, cycloaliphatic groups having generally from 5 to 8 ring atoms, preferably 5 or 6 ring atoms, in which 1, 2 or 3 of the ring carbon atoms are replaced by heteroatoms selected from oxygen, nitrogen, sulfur and an —NR f — group and which is unsubstituted or substituted by one or more, for example 1, 2, 3, 4, 5 or 6 C 1 -C 6 -alkyl groups.
  • R f is preferably hydrogen, alkyl, cycloalkyl, hetero-cycloalkyl, aryl or hetaryl.
  • heterocycloaliphatic groups include 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 comprises unsubstituted or substituted, heteroaromatic, mono- or polycyclic groups, preferably the pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl, purinyl, indazolyl, benzotriazolyl, 1,2,3-triazolyl, 1,3,4-triazolyl and carbazolyl groups, where these heterocycloaromatic groups, in the case of substitution, may bear generally 1, 2 or 3 substituents.
  • the substituents are preferably selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, hydroxyl, carboxyl, halogen and cyano.
  • Nitrogen-containing 5-7-membered heterocycloalkyl or heteroaryl radicals which optionally comprise further heteroatoms selected from oxygen and sulfur comprise, 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.
  • R a and R b radicals specified in the following formulae are as follows:
  • R a and R b radicals are as follows:
  • a further embodiment relates to compounds of the formula (I) where the R a and R b groups are each groups of the formula (A) (so-called swallowtail radicals).
  • the R e radicals are preferably selected from C 4 -C 8 -alkyl, preferably C 5 -C 7 -alkyl.
  • the R a and R b groups are then each a group of the formula
  • # is the bonding site to the imide nitrogen atom and the R e radicals are selected from C 4 -C 8 -alkyl, preferably C 5 -C 7 -alkyl.
  • the R e radicals are then especially linear alkyl radicals which are not interrupted by oxygen atoms.
  • a preferred example of a group of the formula (A) is 1-hexylhept-1-yl.
  • R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals each have a definition other than hydrogen, i.e. compounds of the formula (I) where the R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals are each chlorine and/or fluorine, where 1 or 2 of the R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals may also be cyano.
  • R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals are each chlorine and/or fluorine, where one of the R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals may also be hydrogen.
  • R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals are all chlorine and/or fluorine.
  • R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals are all chlorine or are all fluorine.
  • Perylenetetracarboxylic dianhydrides are referred to hereinafter as compounds (I.A).
  • Perylenetetracarboximides are referred to hereinafter as compounds (I.B), where compounds (I.Ba)
  • a first specific embodiment relates to compounds of the general formula (I.A) where R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 each have the definitions specified above.
  • a further specific embodiment relates to compounds of the general formula (I.Ba) where R a , R b , R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 each have one of the definitions given above.
  • R a and R b radicals are preferably each independently hydrogen or unsubstituted or substituted alkyl, alkenyl, alkadienyl, alkynyl, cycloalkyl, bicycloalkyl, cycloalkenyl, heterocycloalkyl, aryl or heteroaryl.
  • At least one of the R a or R b radicals in the compounds of the formula (I.Ba) is hydrogen. More preferably, both R a and R b are hydrogen.
  • R a and R b radicals are the same.
  • a further specific embodiment relates to compounds of the general formulae (I.Bb1) and (I.Bb2) where R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 each have the definitions given above and X is a divalent bridging group having from 2 to 5 atoms between the flanking bonds.
  • the bridging X groups together with the N—C ⁇ N group to which they are bonded are preferably a 5- to 8-membered heterocycle which is optionally fused once, twice or three times to cycloalkyl, heterocycloalkyl, aryl and/or hetaryl, where the fused groups may each independently bear one, two, three or four substituents selected from alkyl, alkoxy, cycloalkyl, aryl, halogen, hydroxyl, mercapto, COOH, carboxylate, SO 3 H, sulfonate, NE 1 E 2 , alkylene-NE 1 E 2 , nitro and cyano, where E 1 and E 2 are each independently hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, and/or X may have one, two or three substituents which are selected from optionally substituted alkyl, optionally substituted cycloalkyl and optionally substituted aryl
  • the bridging X groups are preferably selected from groups of the formulae (III.a) to (III.d)
  • the R IV , R V , R VI , R VII , R VIII and R IX radicals in the (III.a) to (III.d) groups are each hydrogen.
  • a further specific embodiment relates to compounds of the general formula (I), especially compounds of the formulae (I.A), (I.Ba), (I.Bb1) or (I.Bb2), in which R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 are each fluorine, where 1 or 2 of the R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals may be CN and/or 1 R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radical may be hydrogen. However, preferably all R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals are fluorine.
  • a further specific embodiment relates to compounds of the general formula (I), especially compounds of the formulae (I.A), (I.Ba), (I.Bb1) or (I.Bb2), in which some of the R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals are fluorine and the other R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals are chlorine, where 1 or 2 of the R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals may each be CN and/or 1 R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radical may be hydrogen.
  • R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals are fluorine and the four remaining R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals are chlorine.
  • inventive compounds of the general formula (I) can be prepared proceeding from known compounds with the same perylene base skeleton which, as R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals, have at least one hydrogen atom.
  • the present invention further relates to a process for preparing compounds of the formula (I)
  • R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 , R 24 , Y 1 , Y 2 , Z 1 , Z 2 , Z 3 and Z 4 each have one of the definitions given above, in which
  • inventive compounds of the formula (I) in which the R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals are each chlorine, where one of these radicals may also be hydrogen can be prepared from the corresponding compounds of the formula (II) in which at least one of the R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals is hydrogen by reaction with a chlorinating agent such as thionyl chloride, chlorosulfonic acid, sulfuryl chloride or chlorine in an inert solvent.
  • a chlorinating agent such as thionyl chloride, chlorosulfonic acid, sulfuryl chloride or chlorine in an inert solvent.
  • a particularly preferred embodiment of the present invention relates to the use of chlorosulfonic acid as a solvent (and not as a chlorinating agent) in step a) of the process according to the invention.
  • chlorine is then preferably used as the chlorinating agent.
  • the reaction of the compounds of the formula (II) with a chlorinating agent takes place preferably in the presence of a catalyst.
  • a catalyst include, for example, iodine or iodobenzene, and also mixtures thereof.
  • the compound of the formula (II) is chlorinated by reaction with chlorine in chlorosulfonic acid and in the presence of catalytic amounts of iodine.
  • the reaction temperature for the reaction with a chlorinating agent is typically within a range of from 35 to 110° C., preferably from 40 to 95° C.
  • reaction of the compounds of the formula (II) with a chlorinating agent can be brought about under standard pressure or under elevated pressure.
  • the compounds of the formula (I) are typically isolated from the reaction mixture by precipitation.
  • the precipitation is brought about, for example, by adding a liquid which dissolves the compounds only to a slight degree, if at all, but is miscible with the inert solvents.
  • the precipitation products can then be isolated by filtration and typically have a sufficiently high purity.
  • the product may be advantageous to subject the product to a further purification.
  • a further purification include, for example, column chromatography processes, where the products are subjected to a separation or filtration on silca gel, for example dissolved in a halogenated hydrocarbon such as methylene chloride or a toluene/ethyl acetate or petroleum ether/ethyl acetate mixture.
  • a halogenated hydrocarbon such as methylene chloride or a toluene/ethyl acetate or petroleum ether/ethyl acetate mixture.
  • purification by sublimation or crystallization is possible.
  • the purification steps are repeated once or more than once and/or different purification steps are combined in order to obtain very pure compounds (I).
  • the chlorination of the compound of the formula (II) is brought about by reaction with chlorine in chlorosulfonic acid (as a solvent) and in the presence of catalytic amounts of iodine.
  • the compounds of the formula (I) are preferably isolated by adding water and isolating the solid which precipitates out.
  • the inventive preparation of the compounds of the formula (I) will proceed from the corresponding compounds of the formula (II) in which all R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals are hydrogen, where 1 or 2 of the R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals may also be CN.
  • R 11 to R 14 and R 21 to R 24 are each hydrogen.
  • R a , R b radicals When the R a , R b radicals have aromatic groups, they may also be chlorinated under the chlorinating conditions described above. For this reason, it may be appropriate first to chlorinate the perylene base skeleton and to introduce the R a , R b radicals thereafter, for example by an imidation reaction.
  • the preparation of the inventive compounds of the general formula (I) in which at least some of the R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals are fluorine can proceed from the compounds of the formula (I) which have the same rylene base skeleton and are provided in step a), by partial or full exchange of chlorine for fluorine.
  • Conditions for such a halogen exchange are sufficiently well known to those skilled in the art. Depending on the reaction conditions selected, the halogen exchange can be brought about fully or only partly.
  • compounds of the formula (I) in which at least some of the R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals are fluorine will be prepared by reacting the compound of the formula (I) obtained in step a) with an alkali metal fluoride under essentially anhydrous conditions.
  • essentially anhydrous conditions are understood to mean a total water content, based on all components involved in the reaction (reactants, solvents, complexing agents, etc.), of at most 2% by weight, preferably of at most 1% by weight, especially of at most 0.1% by weight.
  • the components involved in the reaction can be subjected to drying by customary processes known to those skilled in the art.
  • halogen exchange Suitable process conditions for aromatic nucleophilic substitution of chlorine atoms by fluorine atoms (halogen exchange) are known in principle. Suitable conditions for halogen exchange are described, for example, in J. March, Advanced Organic Chemistry, 4th edition, publisher: John Wiley & Sons (1992), p. 659, and in DE 32 35 526.
  • the reaction is an exchange of the chlorine atoms for fluorine atoms.
  • preference is given to using an alkali metal fluoride, especially KF, NaF or CsF.
  • Preferred solvents for the halogen exchange are aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, (CH 3 ) 2 SO, dimethyl sulfone, N,N′-dimethylimidazolidinone or sulfolane. Particular preference is given to using sulfolane as the solvent.
  • the solvents are preferably subjected to drying to remove water by customary methods known to those skilled in the art.
  • suitable solvents such as aromatic hydrocarbons, e.g. xylenes, for example o-xylene.
  • the compound of the formula (I) obtained in step a) will be subjected to halogen exchange in the form of a solution which has a concentration of from 0.002 to 0.2 mol/l, preferably from 0.01 to 0.1 mol/l, in one of the aforementioned solvents.
  • a complexing agent for example a crown ether.
  • a complexing agent for example a crown ether.
  • the complexing agent is selected according to its ability to complex the alkali metals of the alkali metal halides used for the halogen exchange.
  • the complexing agent used is preferably [18]crown-6. Preference is given to using from 0.1 to 10 equivalents of crown ether per equivalent of rylene compound.
  • phase transfer catalysts are, for example, selected from 2-azaallenium compounds, carbophosphazenium compounds, aminophosphonium compounds and diphosphazenium compounds.
  • 2-azaallenium compounds such as (N,N-dimethylimidazolidino)tetramethylguanidinium chloride, are used.
  • the amount of these phase transfer catalysts used is preferably from 0.1 to 20% by weight, preferably from 1 to 10% by weight, based on the weight of the rylene compound used.
  • the reaction temperatures for the halogen exchange are preferably from 100 to 200° C.
  • the reaction time is preferably from 0.5 to 48 hours.
  • suitable compounds are alkali metal cyanides such as KCN and NaCN, and especially zinc cyanide.
  • the reaction is effected preferably in the presence of at least one transition metal catalyst.
  • Suitable transition metal catalysts are especially palladium complexes such as tetrakis(triphenylphosphine)palladium(0), tetrakis(tris-o-tolylphosphine)palladium(0), [1,2-bis(diphenylphosphino)ethane]palladium(II) chloride, [1,1′-bis(diphenylphosphino)-ferrocene]palladium(II) chloride, bis(triethylphosphine)palladium(II) chloride, bis(tricyclohexylphosphine)palladium(II) acetate, (2,2′-bipyridyl)palladium(II) chloride, bis(triphen
  • aromatic hydrocarbons as solvents. These preferably include benzene, toluene, xylenes, etc. Particular preference is given to using toluene.
  • a preferred embodiment of the present invention relates to compounds of the formula (I) in which the Z 1 , Z 2 , Z 3 and Z 4 radicals are each O and to the use thereof.
  • Tetracarboximides of the formulae (I.Ba), (I.Bb1) and (I.Bb2) are preparable by the process according to the invention proceeding from the corresponding rylenetetracarboximides in which at least one of the R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 radicals is hydrogen.
  • the starting materials used for their preparation will, however, be the rylenetetracarboxylic dianhydrides of the formula (II.A) which are known per se.
  • the present invention further relates to processes for preparing compounds of the formula (I.Ba)
  • R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 each have one of the definitions given above, in which
  • the compounds of the formula (I.Ba) can be prepared by a process wherein
  • the present invention further relates to a process for preparing compounds of the formulae (I.Bb1) and/or (I.Bb2),
  • R 11 , R 12 , R 13 , R 14 , R 21 , R 22 , R 23 and R 24 and X each have one of the definitions given above, in which
  • the compounds of the formulae (I.Bb1) and/or (I.Bb2) can be prepared by a process in which
  • Suitable imidation catalysts are organic and inorganic acids, 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, for example, 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 used preferably in the reaction of aromatic amines and is generally also advantageous for the reaction of cycloaliphatic amines.
  • organic acids mentioned above as imidation catalysts are also suitable as solvents.
  • reaction steps 2), 1′), 2′′) and 1′′′) Preference is given to effecting the reaction in reaction steps 2), 1′), 2′′) and 1′′′) under a protective gas atmosphere, for example nitrogen.
  • a protective gas atmosphere for example nitrogen.
  • Reaction steps 2), 1′), 2′′) and 1′′′) can be effected under standard pressure or, if desired, under elevated pressure.
  • a suitable pressure range is in the range from about 0.8 to 10 bar. When volatile amines (boiling point about ⁇ 180° C.) are used, one preferred possibility is use under elevated pressure.
  • the water formed in the reaction in steps 2), 1′), 2′′) and 1′′′) can be removed by distillation by processes known to those skilled in the art.
  • the diamines obtained in reaction step 2), 1′), 2′′) and 1′′′) can be used without further purification.
  • the products it may, however, be advantageous to subject the products to a further purification. This includes, for example, column chromatography processes, in which case the products are preferably dissolved in a halogenated hydrocarbon such as methylene chloride or in an aromatic hydrocarbon, and subjected to a separation or filtration on silica gel.
  • inventive compounds and those obtainable by the process according to the invention are particularly advantageously suitable as organic semiconductors. They generally function as n-semiconductors.
  • the compounds of the formula (I) used in accordance with the invention are combined with other semiconductors and the position of the energy levels causes the other semiconductors to function as n-semiconductors, the compounds (I) may also function as p-semiconductors in exceptional cases.
  • the compounds of the formula (I) are notable for their air stability. Moreover, they have a high charge transport mobility which clearly sets them apart from known organic semiconductor materials. They additionally have a high on/off ratio.
  • the compounds of the formula (I) are particularly advantageously suitable for organic field-effect transistors. They may be used, for example, for the production of integrated circuits (ICs), for which customary n-channel MOSFETs (metal oxide semiconductor field-effect transistors) have been used to date. These are then CMOS-like semiconductor units, for example for microprocessors, microcontrollers, static RAM and other digital logic circuits.
  • ICs integrated circuits
  • MOSFETs metal oxide semiconductor field-effect transistors
  • CMOS-like semiconductor units for example for microprocessors, microcontrollers, static RAM and other digital logic circuits.
  • the compounds of the formula (I) can be processed further by one of the following processes: printing (offset, flexographic, gravure, screenprinting, inkjet, electrophotography), evaporation, laser transfer, photolithography, drop-casting. They are especially suitable for use in displays (specifically large-surface area and/or flexible displays) and RFID tags.
  • the compounds of the formula (I) are particularly advantageously suitable as electron conductors in organic field-effect transistors, organic solar cells and in organic light-emitting diodes. They are also particularly advantageous as an exciton transport material in excitonic solar cells.
  • the compounds of the formula (I) are also particularly advantageously suitable as fluorescent dyes in a display based on fluorescence conversion.
  • Such displays comprise generally a transparent substrate, a fluorescent dye present on the substrate and a radiation source.
  • Typical radiation sources emit blue (color by blue) or UV light (color by uv).
  • the dyes absorb either the blue or the UV light and are used as green emitters.
  • the red light is generated by exciting the red emitter by means of a green emitter which absorbs blue or UV light.
  • Suitable color-by-blue displays are described, for example, in WO 98/28946.
  • Suitable color-by-UV displays are described, for example, by W. A. Crossland, I. D. Sprigle and A. B.
  • the invention further provides organic field-effect transistors comprising a substrate with 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-semiconductor.
  • the invention further provides substrates having a plurality of organic field-effect transistors, wherein at least some of the field-effect transistors comprise at least one compound of the formula (I) as defined above as an n-semiconductor.
  • the invention also provides semiconductor units which comprise at least one such substrate.
  • a specific embodiment is a substrate with a pattern (topography) of organic field-effect transistors, each transistor comprising
  • a further specific embodiment is a substrate having a pattern of organic field-effect transistors, each transistor forming an integrated circuit or being part of an integrated circuit and at least some of the transistors comprising at least one compound of the formula (I).
  • Suitable substrates are in principle the materials known for this purpose.
  • Suitable substrates comprise, for example, 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 (e.g. doped Si, doped Ge), metal alloys (for example based on Au, Ag, Cu, etc.), semiconductor alloys, polymers (e.g.
  • the substrates may be flexible or inflexible, and have a curved or planar geometry, depending on the desired use.
  • a typical substrate for semiconductor units comprises a matrix (for example a quartz or polymer matrix) and, optionally, a dielectric top layer.
  • Suitable dielectrics are SiO 2 , polystyrene, poly- ⁇ -methylstyrene, polyolefins (such as polypropylene, polyethylene, polyisobutene), polyvinylcarbazole, fluorinated polymers (e.g. Cytop), cyanopullulans (e.g. CYMM), polyvinylphenol, poly-p-xylene, polyvinyl chloride, or polymers crosslinkable thermally or by atmospheric moisture.
  • Specific dielectrics are “self-assembled nanodielectrics”, i.e.
  • polymers which are obtained from monomers comprising SiCl functionalities, for example Cl 3 SiOSiCl 3 , Cl 3 Si—(CH 2 ) 6 —SiCl 3 , Cl 3 Si—(CH 2 ) 12 —SiCl 3 , and/or which are crosslinked by atmospheric moisture or by addition of water diluted with 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 to serve as crosslinking components.
  • at least one further polymer to be present during the crosslinking operation, for example polystyrene, which is then also crosslinked (see Facietti, US patent application 2006/0202195).
  • the substrate may additionally have electrodes, such as gate, drain and source electrodes of OFETs, which are normally localized on the substrate (for example deposited onto or embedded into a nonconductive layer on the dielectric).
  • the substrate may additionally comprise conductive gate electrodes of the OFETs, which are typically arranged below the dielectric top layer (i.e. the gate dielectric).
  • an insulator layer (gate insulating layer) is present on at least 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 Al 2 O 3 , Ta 2 O 5 , La 2 O 5 , 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 Al 2 O 3 , Ta 2 O 5 , La 2 O 5 , 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 specific resistance of less than 10 ⁇ 3 ohm ⁇ meter, preferably less than 10 ⁇ 4 ohm ⁇ meter, especially less than 10 ⁇ 6 or 10 ⁇ 7 ohm ⁇ meter.
  • drain and source electrodes are present at least partly on the organic semiconductor material.
  • the substrate may comprise further components as used customarily in semiconductor materials or ICs, such as insulators, resistors, capacitors, conductor tracks, etc.
  • the electrodes may be applied by customary processes, such as evaporation, lithographic processes or another structuring process.
  • the semiconductor materials may also be processed with suitable auxiliaries (polymers, surfactants) in disperse phase by printing.
  • auxiliaries polymers, surfactants
  • the deposition of at least one compound of the general formula (I) is carried out by a gas phase deposition process (physical vapor deposition, PVD).
  • PVD processes are performed under high-vacuum conditions and comprise the following steps: evaporation, transport, deposition.
  • the compounds of the general formula (I) are suitable particularly advantageously for use in a PVD process, since they essentially do not decompose and/or form undesired by-products.
  • the material deposited is obtained in high purity. In a specific embodiment, the deposited material is obtained in the form of crystals or comprises a high crystalline content.
  • At least one compound of the general formula (I) is heated to a temperature above its evaporation temperature and deposited on a substrate by cooling below the crystallization temperature.
  • the temperature of the substrate in the deposition is preferably within a range from about 20 to 250° C., more preferably from 50 to 200° C. It has been found that, surprisingly, elevated substrate temperatures in the deposition of the compounds of the formula (I) can have advantageous effects on the properties of the semiconductor elements achieved.
  • the resulting semiconductor layers generally have a thickness which is sufficient for ohmic contact between source and drain electrodes.
  • the deposition can be effected under an inert atmosphere, for example, under nitrogen, argon or helium.
  • the deposition is effected typically at ambient pressure or under reduced pressure.
  • a suitable pressure range is from about 10 ⁇ 7 , to 1.5 bar.
  • the compound of the formula (I) is preferably deposited on the substrate in a thickness of from 10 to 1000 nm, more preferably from 15 to 250 nm.
  • the compound of the formula (I) is deposited at least partly in crystalline form.
  • the above-described PVD process is suitable.
  • it is possible to use previously prepared organic semiconductor crystals. Suitable processes for obtaining such crystals are described by R. A. Laudise et al.
  • the deposition of at least one compound of the general formula (I) (and optionally further semiconductor materials) is effected by spin-coating.
  • the compounds of the formula (I) used in accordance with the invention should thus also be suitable for producing semiconductor elements, especially OFETs or based on OFETs, by a printing process. It is possible for this purpose to use customary printing processes (inkjet, flexographic, offset, gravure; intaglio printing, nanoprinting).
  • Preferred solvents for the use of compounds of the formula (I) in a printing process are aromatic solvents such as toluene, xylene, etc. It is also possible to add thickening substances such as polymers, for example polystyrene, etc., to these “semiconductor inks”. In this case, the dielectrics used are the aforementioned compounds.
  • the inventive field-effect transistor is a thin-film transistor (TFT).
  • TFT thin-film transistor
  • a thin-film transistor has a gate electrode disposed on the substrate, a gate insulation layer disposed thereon and on the substrate, a semiconductor layer disposed on the gate insulator 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 before the deposition of at least one compound of the general formula (I) (and optionally of at least one further semiconductor material), is subjected to a modification.
  • This modification serves to form regions which bind the semiconductor materials and/or regions on which no semiconductor materials can be deposited.
  • the surface of the substrate is preferably modified 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 portion of the surface or the complete surface of the substrate is coated with at least one compound (C1) in order to enable improved deposition of at least one compound of the general formula (I) (and optionally further semiconductive compounds).
  • a further embodiment comprises the deposition of a pattern of compounds of the general formula (C1) on the substrate by a corresponding production process.
  • These include the mask processes known for this purpose and so-called “patterning” processes, as described, for example, in U.S. Ser. No. 11/353,934, which is incorporated here fully by reference.
  • 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 comprises the formation of a chemical bond (covalent bond), ionic bond, coordinative interaction, van der Waals interactions, e.g. dipole-dipole interactions etc.), and combinations thereof.
  • Suitable compounds of the general formula (C1) are:
  • the compound (C1) is preferably selected from alkyltrialkoxysilanes, especially n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane; hexaalkyldisilazanes, and especially hexamethyldisilazane (HMDS); C 8 -C 30 -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
  • top contact for example top contact, top gate, bottom contact, bottom gate, or else a vertical construction, for example a VOFET (vertical organic field-effect transistor), as described, for example, in US 2004/0046182.
  • VOFET vertical organic field-effect transistor
  • the layer thicknesses are, for example, from 10 nm to 5 ⁇ m in semiconductors, from 50 nm to 10 ⁇ m in the dielectric; the electrodes may, for example, be from 20 nm to 1 ⁇ m.
  • the OFETs may also be combined to form other components such as ring oscillators or inverters.
  • a further aspect of the invention is the provision of electronic components which comprise a plurality of semiconductor components, which may be n- and/or p-semiconductors.
  • semiconductor components which may be n- and/or p-semiconductors.
  • FETs field-effect transistors
  • BJTs bipolar junction transistors
  • tunnel diodes converters
  • light-emitting components 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, timer units, static or dynamic stores and other dynamic or sequential, logical or other digital components including programmable switches.
  • a specific semiconductor element is an inverter.
  • the inverter is a gate which inverts an input signal.
  • the inverter is also referred to as a NOT gate.
  • Real inverter switches have an output current which constitutes the opposite of the input current. Typical values are, for example, (0, +5V) for TTL switches.
  • the performance of a digital inverter reproduces the voltage transfer curve (VTC), i.e. the plot of input current against output current. Ideally, it is a staged function and, the closer the real measured curve approximates to such a stage, the better the inverter is.
  • VTC voltage transfer curve
  • the compounds of the formula (I) are used as organic n-semiconductors in an inverter.
  • the compounds of the formula (I) are also particularly advantageously suitable for use in organic photovoltaics (OPVs). These compounds are preferably suitable for use in solar cells which are characterized by diffusion of excited states (exciton diffusion). In this case, one or both of the semiconductor materials utilized is notable for a diffusion of excited states (exciton mobility). Also suitable is the combination of at least one semiconductor material which is characterized by diffusion of excited states with polymers which permit conduction of the excited states along the polymer chain. In the context of the invention, such solar cells are referred to as excitonic solar cells. The direct conversion of solar energy to electrical energy in solar cells is based on the internal photo effect of a semiconductor material, i.e.
  • An exciton can form, for example, when a photon penetrates into a semiconductor and excites an electron to transfer from the valence band into the conduction band.
  • the excited state generated by the absorbed photons must, however, reach a p-n transition in order to generate a hole and an electron which then flow to the anode and cathode.
  • the photovoltage thus generated can bring about a photocurrent in an external circuit, through which the solar cell delivers its power.
  • the semiconductor can absorb only those photons which have an energy which is greater than its band gap.
  • the size of the semiconductor band gap thus determines the proportion of sunlight which can be converted to electrical energy.
  • Solar cells consist normally of two absorbing materials with different band gaps in order to very effectively utilize the solar energy.
  • Most organic semiconductors have exciton diffusion lengths of up to 10 nm. There is still a need here for organic semiconductors through which the excited state can be passed on over very large distances. It has now been found that, surprisingly, the compounds of the general formula (I) described above are particularly advantageously suitable for use in excitonic solar cells.
  • Suitable organic solar cells generally have a layer structure and generally comprise at least the following layers: anode, photoactive layer and cathode. These layers generally consist of a substrate customary therefor.
  • the structure of organic solar cells is described, for example, in US 2005/0098726 A1 and US 2005/0224905 A1, which are fully incorporated here by reference.
  • Suitable substrates are, for example, oxidic materials (such as glass, ceramic, SiO 2 , especially quartz, etc.), polymers (e.g. polyvinyl chloride, polyolefins such as polyethylene and polypropylene, polyesters, fluoropolymers, polyamides, polyurethanes, polyalkyl (meth)acrylates, polystyrene and mixtures and composites thereof) and combinations thereof.
  • oxidic materials such as glass, ceramic, SiO 2 , especially quartz, etc.
  • polymers e.g. polyvinyl chloride, polyolefins such as polyethylene and polypropylene, polyesters, fluoropolymers, polyamides, polyurethanes, polyalkyl (meth)acrylates, polystyrene and mixtures and composites thereof.
  • the cathode used is preferably a material which essentially reflects the incident light. This includes, for example, metal films, for example of Al, Ag, Au, In, Mg, Mg/Al, Ca, etc.
  • Suitable exciton blocker layers are, for example, bathocuproins (BCPs), 4,4′,4′′-tris[3-methylphenyl(phenyl)amino]triphenylamine (m-MTDATA) or polyethylenedioxy-thiophene (PEDOT), as described in U.S. Pat. No. 7,026,041.
  • BCPs bathocuproins
  • m-MTDATA 4,4′,4′′-tris[3-methylphenyl(phenyl)amino]triphenylamine
  • PEDOT polyethylenedioxy-thiophene
  • the inventive excitonic solar cells are based on photoactive donor-acceptor heterojunctions.
  • HTM hole transport material
  • ETM exciton transport material
  • Suitable ETMs are, for example, C60 and other fullerenes, perylene-3,4:9,10-bis(dicarboximides) (PTCDIs), etc.
  • PTCDIs perylene-3,4:9,10-bis(dicarboximides)
  • the complementary HTM must be selected such that, after excitation, a rapid hole transfer to the HTM takes place.
  • the heterojunction may have a flat configuration (cf.
  • Thin layers of the compounds and of all other layers can be produced by vapor deposition under reduced pressure or in inert gas atmosphere, by laser ablation or by solution- or dispersion-processable methods such as spin-coating, knife-coating, casting methods, spraying, dip-coating or printing (e.g. inkjet, flexographic, offset, gravure; intaglio, nanoimprinting).
  • the layer thicknesses of the M, n, i and p layers are typically from 10 to 1000 nm, preferably from 10 to 400 nm.
  • the substrates used are, for example, glass, metal foils or polymer films which are generally coated with a transparent conductive layer (for example SnO 2 :F, SnO 2 :In, ZnO:Al, carbon nanotubes, thin metal layers).
  • a transparent conductive layer for example SnO 2 :F, SnO 2 :In, ZnO:Al, carbon nanotubes, thin metal layers.
  • Phthalocyanines such as hexadecachlorophthalocyanines and hexadecafluorophthalocyanines, metal-free phthalocyanines and phthalocyanines comprising divalent metals or metal atom-containing groups, especially those of titanyloxy, vanadyloxy, iron, copper, zinc, etc.
  • Suitable phthalocyanines are especially copper phthalocyanine, zinc phthalocyanine, metal-free phthalocyanine, copper hexadecachlorophthalocyanine, zinc hexadecachlorophthalocyanine, metal-free hexadecachlorophthalocyanine, copper hexadecafluorophthalocyanine, hexadecafluorophthalocyanine or metal-free hexadecafluorophthalocyanine.
  • Porphyrins for example 5, 10,15,20-tetra(3-pyridyl)porphyrin (TpyP), or else tetrabenzoporphyrins, for example metal-free tetrabenzoporphyrin, copper tetrabenzoporphyrin or zinc tetrabenzoporphyrin.
  • TpyP 10,15,20-tetra(3-pyridyl)porphyrin
  • tetrabenzoporphyrins for example metal-free tetrabenzoporphyrin, copper tetrabenzoporphyrin or zinc tetrabenzoporphyrin.
  • Liquid-crystalline (LC) materials for example coronenes, such as hexabenzocoronene (HBC-PhC12), coronenediimides, or triphenylenes such as 2,3,6,7,10,11-hexahexylthiotriphenylene (HTT 6 ), 2,3,6,7,10,11-hexakis(4-n-nonylphenyl)triphenylene (PTP 9 ) or 2,3,6,7,10,11-hexakis(undecyloxy)triphenylene (HAT 11 ). Particular preference is given to liquid-crystalline materials which are discotic.
  • coronenes such as hexabenzocoronene (HBC-PhC12), coronenediimides, or triphenylenes
  • HCT 6 2,3,6,7,10,11-hexahexylthiotriphenylene
  • PTP 9 2,3,6,7,10,11-hexakis(4-n-nonyl
  • oligothiophenes are quaterthiophenes, quinquethiophenes, sexithiophenes, ⁇ , ⁇ -di(C 1 -C 8 )alkyloligothiophenes such as ⁇ , ⁇ -dihexylquaterthiophenes, ⁇ , ⁇ -dihexyl-quinquethiophenes and ⁇ , ⁇ -dihexylsexithiophenes, poly(alkylthiophenes) such as poly(3-hexylthiophene), bis(dithienothiophenes), anthradithiophenes and dialkylanthradithiophenes such as dihexylanthradithiophene, phenylene-thiophene (P-T) oligomers and derivatives thereof, especially ⁇ , ⁇ -alkyl-substi
  • DCV 5 T 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), poly(pyridopyrazinevinylene)-polythiophene blends such as EHH-PpyPz, PTPTB copolymers, BBL, poly(9,9-dioctyl-fluorene-co-bis-N,N′-(4-methoxyphenyl)bis-N,N′-phenyl
  • PCPDTBT poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-M-dithiophene)-4,7-(2,1,3-benzothiadiazole);
  • Paraphenylenevinylene and paraphenylenevinylene-comprising oligomers and polymers for example polyparaphenylenevinylene (PPV), MEH-PPV (poly(2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene)), MDMO-PPV (poly(2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene)), cyano-paraphenylenevinylene (CN-PPV), CN-PPV modified with various alkoxy groups; Phenyleneethynylene/phenylenevinylene Hybrid Polymers (PPE-PPV).
  • PPE-PPV polyparaphenylenevinylene
  • MEH-PPV poly(2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene)
  • MDMO-PPV poly(2-methoxy-5
  • Polyfluorenes and alternating polyfluorene copolymers for example with 4,7-dithien-2′-yl-2,1,3-benzothiadiazole.
  • 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 i.e. carbazole-comprising oligomers and polymers, such as (2,7) and (3,6).
  • Polyanilines i.e. aniline-comprising oligomers and polymers.
  • Triarylamines polytriarylamines, polycyclopentadienes, polypyrroles, polyfurans, polysiloles, 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-methoxyphenyl-amine)-9,9′-spirobifluorene (Spiro-MeOTAD).
  • TPD N,N′-bis(3-methylphenyl)-N,N′-bis(phenyl)benzidine
  • CBP 4,4′-bis(carbazol-9-yl)biphenyl
  • Spiro-MeOTAD 2,2′,7,7′-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,9′
  • the fullerene derivative is a hole conductor.
  • All aforementioned semiconductor materials may also be doped.
  • suitable dopants for n-semiconductors are, for example, the compounds of the formula (I), rhodamine or pyronin B.
  • suitable dopants for p-semiconductors are 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F 4 -TCNQ).
  • the invention further provides an organic light-emitting diode (OLED) which comprises at least one compound of the general formula (I) as defined above.
  • OLED organic light-emitting diode
  • the compounds of the formula (I) may serve as a charge transport material (electron conductor).
  • Organic light-emitting diodes are in principle constructed from 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 organic 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 likewise suitable, in which case the functions of the layers (2) (hole-transporting layer) and (4) (electron-transporting layer) are assumed by the adjacent layers. OLEDs which have the layers (1), (2), (3) and (5) or the layers (1), (3), (4) and (5) are likewise suitable.
  • OLEDs can be produced by methods known to those skilled in the art. In general, an OLED is produced by successive vapor deposition of the individual layers onto a suitable substrate. Suitable substrates are, for example, glass or polymer films. For vapor deposition, it is possible to use customary techniques such as thermal evaporation, chemical vapor deposition and others.
  • the organic layers may be coated from solutions or dispersions in suitable solvents, for which coating techniques known to those skilled in the art are employed.
  • Compositions which, as well as a compound of the general formula (I) have a polymeric material in one of the layers of the OLED, preferably in the light-emitting layer, are generally applied as a layer by processing from solution.
  • the inventive OLEDs can be used in all devices in which electroluminescence is useful. Suitable devices are preferably selected from stationary and mobile visual display units. Stationary visual display units are, for example, visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, illuminations and information panels. Mobile visual display units are, for example, visual display units in cellphones, laptops, digital cameras, vehicles and destination displays on buses and trains.
  • the compounds (I) may be used in OLEDs with inverse structure.
  • the compounds (I) in these inverse OLEDs are in turn preferably used in the light-emitting layer.
  • the structure of inverse OLEDs and the materials typically used therein are known to those skilled in the art.
  • Suitable purification processes comprise conversion of the compounds of the formula (I) to the gas phase. This includes purification 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. Preference is given to subliming the compound of the formula (I) with heating in a carrier gas stream. The carrier gas then flows through a separating chamber. A suitable separating chamber has at least two different separating zones with different temperatures. Preference is given to using a three-zone furnace. A suitable process and an apparatus for fractional sublimation is described in U.S. Pat. No. 4,036,594.
  • the invention further provides a process for depositing at least one compound of the formula (I) onto or applying at least one compound of the formula (I) to a substrate by a gas phase deposition process or a wet application process.
  • the compound was purified further by recrystallization from toluene. To this end, 4.0 g of the crude product in toluene (1.1 l) were heated under reflux and cooled to 0° C. for several days. The precipitated solid was filtered off and dried under reduced pressure. This afforded 3.21 g of the purified compound.
  • the product was purified further by recrystallization. To this end, 4.0 g of the crude product were dissolved in N-methylpyrrolidone (NMP, 70 ml) at 140° C., and the mixture was cooled slowly to room temperature. The precipitate was isolated by filtration, washed with petroleum ether and dried under reduced pressure. Subsequently, the residue was taken up in acetic acid for several days and stirred under reflux conditions. After another filtration and drying, 0.81 g of purified octachloro-N,N′-dihydroperylene-3,4:9,10-tetracarboximide was obtained (chlorine content: 42.7% (theor.: 42.6%)).
  • NMP N-methylpyrrolidone
  • Octachloro-N,N′-bis(2,6-diisopropyl-phenyl)perylene-3,4:9,10-tetracarboximide was obtained as an orange solid in an amount of 0.6 g (40% yield).
  • R f (SiO 2 , toluene/ethyl acetate, 10:1) 0.86.
  • N,N′-bis(1H, 1H-perfluorobutyl)-1,6,7,12-tetrachloroperylene-3,4:9,10-tetracarboximide was obtained as a product mixture with the corresponding trichlorinated perylene, as an orange solid, in an amount of 12.83 g (81% yield).
  • R f (toluene) 0.39.
  • the chlorination was effected analogously to example 11.b, except that a total of 212 g of chlorine were introduced in portions at 60° C. over a period of four days.
  • the reaction mixture was added to ice-water, filtered, washed to neutrality with water and dried under reduced pressure.
  • 6.0 g of an orange crude product were purified by column chromatography (column with a diameter of 6.5 cm) on 180 g of silica gel with 1:1 toluene/petroleum ether. This gave 3.8 g of pure title compound.
  • R f (toluene) 0.72.
  • the coated substrates were cleaned by rinsing with acetone and isopropanol.
  • the semiconductor compounds were applied by vapor deposition under reduced pressure at defined deposition temperatures between 25 and 150° C. (typically at 125° C.), and deposited on the substrate with a deposition rate in the range from 0.3 to 0.5 ⁇ /s and a pressure of 10 ⁇ 6 Torr in a vacuum coating apparatus (Angstrom Engineering Inc., Canada).
  • TFTs were provided in top-contact configuration.
  • source and drain electrodes of gold typically of channel length 100 ⁇ m and length/width ratio about 20
  • the electrical properties of the TFTs were determined by means of a Keithley 4200-SCS semiconductor parameter analyzer.
  • the surface can additionally be modified, for example, with n-octadecyltriethoxysilane (OTS, C 18 H 37 Si(OC 2 H 5 ) 3 ).
  • OTS n-octadecyltriethoxysilane
  • a few drops of OTS were placed onto the preheated surface (about 100° C.) in a vacuum desiccator.
  • the desiccator was evacuated and the substrates were kept under reduced pressure (25 mm Hg) for at least 5 hours. Finally, the substrates were baked at 110° C. for 15 minutes, rinsed with isopropanol and dried in a nitrogen stream.
  • SiO 2 /Si substrates were rinsed with toluene, acetone and isopropanol, and dried in a nitrogen stream. The cleaned wafers were used without further surface modification.
  • the compounds are purified by three-zone gradient sublimation.
  • the compound was deposited at 125° C.
  • the component was analyzed both under nitrogen and in an air atmosphere. The results are listed in table 1.
  • the compound was deposited at 125° C.
  • the component was analyzed both under nitrogen and in an air atmosphere. The results are listed in table 2.
  • the compound was deposited at 125° C.
  • the component was analyzed both under nitrogen and in an air atmosphere. The results are listed in table 3.

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CN101809116B (zh) 2014-03-19
WO2009024512A1 (de) 2009-02-26
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KR101580338B1 (ko) 2015-12-23
US8674104B2 (en) 2014-03-18
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