DE102013205093A1 - New substituted tetraheterocyclic compounds useful in optoelectronic or electronic components, preferably e.g. organic light-emitting diodes, organic solar cells, dye-sensitized solar cells, batteries and accumulators, and organic diodes - Google Patents

Abstract

Substituted tetraheterocyclic compounds (I) are new. Substituted tetraheterocyclic compounds of formula (I) are new. Y1, Y2 : =NCN-, =C(CN) 2-, =C(CF 3)R-, =C(C 6F 5) 2-, =C(heteroaryl) 2-, =C(CF 3) 2-, =C(CN)R- or =C(CN)(CF 3)-; R : H, halo, CN, NO 2, nitroso, sulfamide, carboxy, 1-20C carbo-alkoxy, 1-20C sulfo-alkyl, sulfo-halo-, sulfonic acid, electron deficient (hetero)aromatic group, halocarbonyl, carbamoyl, formyl, amidine-formyl, 1-6C alkylsulfanyl, 1-20C alkylsulfonyl or optionally saturated or aromatic 1-20C hydrocarbyl (all optionally substituted by at least one R) or hydrocarbyl moiety of formula (II); Xa-Xe : N or C (substituted by R21); R21 : R; X1-X4, X7-X14 : N or C (substituted by R1-R4 or R7-R14); R1-R4, R7-R14 : H, halo, CN, NO 2, nitroso, sulfamide carboxy, 1-20C carbo-alkoxy, 1-20C sulfo-alkyl, =O, sulfo-halo, halocarbonyl, carbamoyl, formyl, amidine-formyl, 1-6C alkylsulfanyl, 1-20C alkylsulfonyl or optionally saturated or aromatic 1-20C hydrocarbyl (all optionally substituted by R1-R4 or R7-R14); X5 : C (substituted by R5 or R6), N or C=Y3 (IIa); X6 : C (substituted by R5 or R6), N or C=Y4 (IIb); R5, R6 : R1-R4 or R7-R14; and Y3, Y4 : Y1, Y2. Provided that when X5 is (IIa) and X6 is (IIb), then groups X11-X14 or groups X5, X6 and X11-X14 are not present in (I). [Image].

Description

The invention relates to novel organic quinoid N-heterocycles, quinoid N-Heteropolyzyklen and quinoid phenanthrene derivatives and their preparation and use, in particular as dopants for organic semiconducting matrix materials.

In recent decades, it has become known that one can greatly influence organic semiconductors by doping in terms of their electrical conductivity. Such organic semiconductive matrix materials can be constructed from either compounds with good electron donating properties or from compounds having good electron acceptor properties. In addition to inorganic Lewis acids, doping of electron donor materials (HTM) has also been reported to include strong organic electron acceptors such as tetracyanoquinonedimethane (TCNQ) or 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinone dimethyne (F4TCNQ) [ M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (22), 3202-3204 (1998) and J. Blochwitz, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (6), 729-731 (1998) ]. These generate so-called holes by electron transfer processes in electron-rich base materials (hole transport materials), whose number and mobility changes the conductivity of the base material more or less significantly. Suitable matrix materials with hole transport properties are, for example, N, N'-perarylated benzidines (TPD) or N, N ', N "perarylated starburst compounds, such as the substance TDATA, bridged triarylamines, electron-rich spiro compounds, thiophenes (preferably oligo-thiophenes), aminothiophenes or but also certain metal phthalocyanines, in particular zinc phthalocyanine ZnPc.

Also known to date are also quinoid bisimidazoles and their derivatives, which are used as dopants for organic semiconductive matrix materials ( EP 1 990 847 A1 ). Similarly, the US patent US 6,908,783 B1 Dotands for organic semiconducting matrix materials based on quinones and their derivatives as well as on 1,2,3-dioxaborines or their derivatives. Further dopants based on specific quinones are used, for example, by Gao et al. in Chem. Commun., 2008, 117-119 shown.

However, the compounds described so far have disadvantages in the production of doped semiconductive organic layers or of corresponding electronic components with such doped layers for a technical application, since the manufacturing processes in large-scale production plants or those on a pilot plant scale can not always be controlled with sufficient precision. This leads to high control and regulation costs within the processes in order to achieve a desired product quality or to undesired tolerances of the products. Furthermore, there are disadvantages in the use of previously known organic donors with respect to the electronic component structures such as light-emitting diodes (OLEDs), organic field effect transistor (OFET) or solar cells themselves, since the mentioned production difficulties in handling the dopants to unwanted irregularities in the electronic components or unwanted aging effects of the electronic Can lead components. At the same time, however, it should be noted that the dopants to be used have extremely high electron affinities (reduction potentials) and other properties suitable for the application, since, for example, the dopants also determine the conductivity or other electrical properties of the organic semiconductive layer under given conditions. Normally, the energetic layers of the HOMO of the matrix material and the LUMO of the dopant are crucial for the doping effect, which have proven to be in the hitherto known compounds in need of improvement. There are also doping effects that can not be explained with the current knowledge. Certainly, molecular and layer structures and the associated distances between the centers of the electron-donor and acceptor molecules are also important for the electrical doping effect, which can hardly be predicted.

The object of the present invention was the provision of new substances which can be used as dopants for organic semiconductive matrix materials. These should be easier to handle in the production process and lead to electronic components whose organic semiconducting materials can be produced more reproducibly.

The object is achieved by quinoid N-heterocycles, quinoid N-Heteropolyzyklen and quinoid phenanthrene derivatives according to claim 1-8 and by the use according to claims 9 and 10. Further preferred embodiments will be apparent from the dependent claims.

wobei
Y1 und Y2 gleich oder verschieden sind und jeweils unabhängig voneinander für einen =NCN, =C(CN)₂, =C₆H₄=C(CN)₂, =C6F4=C(CN)2, =C5H3N=C(CN)2, =C6F2(CN)2=C(CN)2, =C5H2N2=C(CN)2 =C(CF₃)R, =C(CF₃)₂,=C(C₆F₅)₂, =C(Heteroaryl)₂, =C(CN)R oder =C(CN)(CF₃)-Rest, wobei die Reste
R ausgewählt sind aus der Gruppe von Wasserstoff, Halogen-, Cyano-, Nitro-, Nitroso-, Sulfamid- Carboxy-, C1-C20-Carbalkoxy-, C1-C20-Alkylsulfo-, Sulfohalogen-, Sulfonsäure-Gruppe (-SO₃H), elektronenarmen Aromaten oder Heteroaromaten, insbesondere halogenierten oder/und cyanierten Aromaten und Heteroaromaten, wie Pentafluorophenyl, Cyanoperfluorophenyl, Dicyanoperfluorophenylen, Perfluorobiphenyl, Perfluoropyridin, Perchloropyridin, Halogencarbonyl-, Carbamoyl-, Formyl-, Amidinformyl-, C1-C6-Alkylsulfanyl- und C1-C20-Alkylsulfonyl-Rest und C1-C20-Kohlenwasserstoff, wobei eines oder mehrere oder alle Kohlenstoffatome gegebenenfalls mit einem oder mehreren der oben genannten Reste weiter substituiert ist/sind und wobei der Kohlenwasserstoff gesättigt, ungesättigt oder ein aromatischer Kohlenwasserstoff, vorzugsweise ein vollständig oder unvollständig halogenierter C2-C20-Alkylrest, besonders bevorzugt ein perfluorierter C2-C20-Alkylrest ist,
oder für eine Gruppe der allgemeinen Formel II stehen,

wobei
Xa–Xe gleich oder verschieden sind und jeweils unabhängig voneinander ein Stickstoffatom oder ein Kohlenstoffatom sind, wobei die Kohlenstoffatome Reste Ra–e tragen, welche gleich oder verschieden sind und jeweils unabhängig voneinander aus der gleichen Gruppe wie R ausgewählt sind und wobei
X1–X4 und X7–X14 gleich oder verschieden sind und jeweils unabhängig voneinander ein Stickstoffatom oder ein Kohlenstoffatom sind,
wobei die Kohlenstoffatome bei X1–X4 und X7–X14 Reste R1–R4 und R7–R14 tragen, welche gleich oder verschieden sind und jeweils unabhängig voneinander ausgewählt sind aus der Gruppe von Wasserstoff, Halogen-, vorzugsweise Fluor, Cyano-, Nitro-, Nitroso-, Sulfamid- Carboxy-, C1-C20-Carbalkoxy-, C1-C20-Alkylsulfo-, =O, Sulfohalogen-, Halogencarbonyl-, Carbamoyl-, Formyl-, Amidinformyl-, C1-C6-Alkylsulfanyl- und C1-C20-Alkylsulfonyl-Rest und C1-C20-Kohlenwasserstoff, wobei eines oder mehrere oder alle Kohlenstoffatome gegebenenfalls mit einem oder mehreren der oben genannten Reste weiter substituiert ist/sind und wobei der Kohlenwasserstoff gesättigt, ungesättigt oder ein aromatischer Kohlenwasserstoff ist
und
wobei
X5 und X6 gleich oder verschieden sind und jeweils unabhängig voneinander ein Stickstoffatom oder ein Kohlenstoffatom sind,
wobei die Kohlenstoffatome Reste R5, R6 tragen, welche gleich oder verschieden sind und jeweils unabhängig voneinander ausgewählt sind aus der gleichen Gruppe wie R1–R4 und R7–R14,
oder
X5, X6 jeweils für einen C=Y³-Rest (X5), C=Y⁴-Rest (X6) stehen, wobei Y3, 4 jeweils unabhängig aus der gleichen Gruppen wie Y1, 2 ausgewählt sind, und in diesem Fall X11–X14 entfallen
oder
X11 entfällt
oder
X5, X6 und X11–X14 entfallen. In other words, the object is achieved by quinoid N-heterocycles, quinoid N-Heteropolyzyklen and quinoid phenanthrene derivatives of general formula I,

in which
Y1 and Y2 are the same or different and each independently represent a = NCN, = C (CN) _2, = C ₆ H ₄ = C (CN) _2, = C6F4 = C (CN) 2, = C5H3N = C (CN ) 2, = C ₆ F ₂ (CN) 2 = C (CN) 2, = C 5 H 2 N 2 = C (CN) 2 = C (CF ₃ ) R, = C (CF ₃ ) ₂ , = C (C ₆ F ₅ ) ₂ , = C (heteroaryl) ₂ , = C (CN) R or = C (CN) (CF ₃ ) radical, where the radicals
R are selected from the group of hydrogen, halogen, cyano, nitro, nitroso, sulfamide-carboxy, C 1 -C 20 -carbalkoxy, C 1 -C 20 -alkylsulfo, sulfo-halo, sulfonic acid (-SO ₃ H), electron-poor aromatic or heteroaromatic, in particular halogenated and / or cyanated aromatics and heteroaromatics, such as pentafluorophenyl, Cyanoperfluorophenyl, Dicyanoperfluorophenylen, perfluorobiphenyl, perfluoropyridine, perchloropyridine, halocarbonyl, carbamoyl, formyl, Amidinformyl-, C1-C6-alkylsulfanyl- and C 1 -C 20 -alkylsulfonyl radical and C 1 -C 20 -hydrocarbon wherein one or more or all carbon atoms are optionally further substituted by one or more of the abovementioned radicals and wherein the hydrocarbon is saturated, unsaturated or an aromatic hydrocarbon, preferably a complete one or C.sub.2-C.sub.20-alkyl radical which is not completely halogenated, particularly preferably a perfluorinated C.sub.2-C.sub.20-alkyl radical,
or represents a group of the general formula II,

in which
Xa-Xe are the same or different and each independently is a nitrogen atom or a carbon atom, wherein the carbon atoms carry radicals Ra-e which are the same or different and are each independently selected from the same group as R and wherein
X1-X4 and X7-X14 are the same or different and each independently is a nitrogen atom or a carbon atom,
wherein the carbon atoms in X1-X4 and X7-X14 carry radicals R1-R4 and R7-R14 which are identical or different and are each independently selected from the group of hydrogen, halogen, preferably fluorine, cyano, nitro, Nitroso, sulfamide carboxy, C1-C20 carbalkoxy, C1-C20 alkyl sulfo, = O, sulfohalo, halocarbonyl, carbamoyl, formyl, amidinoformyl, C1-C6 alkylsulfanyl and C1-C20 Alkylsulfonyl radical and C 1 -C 20 -hydrocarbon wherein one or more or all of the carbon atoms are optionally further substituted by one or more of the abovementioned radicals and wherein the hydrocarbon is saturated, unsaturated or an aromatic hydrocarbon
and
in which
X5 and X6 are the same or different and each independently is a nitrogen atom or a carbon atom,
wherein the carbon atoms carry radicals R5, R6 which are identical or different and are each independently selected from the same group as R1-R4 and R7-R14,
or
X5, X6 are each a C = Y ³ radical (X5), C = Y ⁴ radical (X 6), where Y ³ , 4 are each independently selected from the same groups as Y 1, 2, and in this case X 11- X14 omitted
or
X11 is omitted
or
X5, X6 and X11-X14 are eliminated.

Such quinoid N-heterocycles, quinoid N-Heteropolyzyklen and quinoid phenanthrene derivatives of general formula I are unknown. In particular, planar N-heterocyclic quinone derivatives are described as very unstable and hardly synthesizable.

Surprisingly, it has been shown that in the compounds according to the invention the position of the LUMO is so low that further technically interesting HT materials can now be efficiently doped only now. Due to the exceptionally low LUMO position and the associated high reduction potential of the quinoid phenanthrene derivatives and the N-heterocyclic quinone derivatives, performance efficiencies of solar cells can be significantly improved. Additionally, due to their size and high polarity, these compounds are exceptionally diffusional in organic layers. The concentration of dopant and concomitant efficiency-reducing self-absorption can be significantly improved.

In the case of halogen as radicals R1-R4 and R7-R14, in particular fluorine and chlorine are preferred. Sulfamides as radicals R1-R4 and R7-R14 are unsubstituted or substituted, preferably substituted by C1-C20 mono- or di-alkyl groups. Sulfohalogen or halocarbonyl radicals R1-R4 and R7-R14 have in particular fluorine or chlorine as halogen. Carbamoyl radicals are unsubstituted or substituted, in particular N-C 1 -C 6 -monoalkyl-substituted or identical or independently of one another N-C 1 -C 20 -dialkyl-substituted. C1-C20 hydrocarbons are preferably C1-C20 hydrocarbons which are unsubstituted or substituted, wherein one or more or all of the carbon atoms of the group may be further substituted with one or more of the above radicals, wherein the hydrocarbon is saturated, unsubstituted or is an aromatic hydrocarbon. The hydrocarbon groups are in particular perhalogenated, preferably perchlorinated or perfluorinated, more preferably perfluorinated (in particular trifluoromethyl). The hydrocarbon groups are linear or branched or cyclic and / or fluorinated, for example cyclohexyl / C6F11 or cyclopentyl / C5F9. One or more carbon atoms may each be replaced by heteroatoms, in particular N, O, S, - (O) S (O) - or P (R) (R = perfluoroalkyl, alkyl, aryl, heteroaryl). The (hetero) hydrocarbon radicals may be cyclically linked to one another or to a quinoid or other ring, for example a (hetero) aryl ring.

In particular, the radicals R1-R4 and R7-R14 are selected from the group of acetyl, trifluoroacetyl, benzoyl, pentafluorobenzoyl, naphthoyl, alkoxycarbonyl group, where the alkyl radical is an alkyl having one to six, in particular one to four, straight-chain or branched C atoms, as well as trialkylphosphoryl group with alkyl radicals which likewise consist of a chain having 1 to 20 unbranched or branched or cyclically linked carbon atoms, preferably 6 to 14 C atoms, particularly preferably 6 to 8 C -atoms.

Furthermore, the radicals R 1 -R 4 and R 7 -R 14, which may be identical or different, may be either aryl radicals or heterocyclic radicals. These are preferably selected from the group of phenyl, naphthyl, anthranyl, pyridyl, quinoxalyl, pyrazolyl, oxazolyl, 1,3,2-dioxaborinyl and 1,3,4-oxadiazolyl, which are either hydrogen or further substituents from the group of functional Group, halogen or a lower alkyl or haloalkyl radical having one to 20 saturated carbon atoms which are unbranched or branched or cyclically bonded together, are substituted.

From the latter group of further substituents halogens or haloalkyls are preferred, above all fluorine or chlorine, trichloromethyl, perfluoroalkyl having one to six carbon atoms, in particular trifluoromethyl, but also functional groups such as cyano, nitro, nitroso, sulfo, carboxy, Carbalkoxy, halocarbonyl, carbamoyl, formyl, amidinoformyl, alkylsulfanyl and alkylsulfonyl, wherein the alkyl radicals here again consist of a chain having one to eight, preferably 1 to 6, more preferably 1 to 5, unbranched or branched or cyclically linked carbon atoms, and trialkylphosphoryl Radicals having alkyl radicals, which likewise consist of a chain having one to twenty, preferably one to 6, more preferably 1 to 5, unbranched or branched, linked together carbon atoms.

wobei
Y1, 2 und Y3, 4 die zur allgemeinen Formel I genannte Bedeutung von Y1, 2 haben und Y3 und Y4 können zusätzlich noch eine Carboxy-(=O)-Gruppe darstellen und wobei
X1–X4 und X7–X10 gleich oder verschieden sind und jeweils unabhängig voneinander ein Stickstoffatom oder ein Kohlenstoffatom sind, wobei die Kohlenstoffatome bei X1–X10 Reste R1–10 tragen, welche gleich oder verschieden sind und jeweils unabhängig voneinander ausgewählt sind aus der Gruppe von Wasserstoff Halogen-, Cyano-, Nitro-, Nitroso-, Sulfamid- Carboxy-, C1-C20-Carbalkoxy-, C1-C20-Alkylsulfo-, =O, Sulfohalogen-, Halogencarbonyl-, Carbamoyl-, Formyl-, Amidinformyl-, C1-C6-Alkylsulfanyl-und C1-C20-Alkylsulfonyl-Rest und C1-C20-Kohlenwasserstoff, wobei eines oder mehrere oder alle Kohlenstoffatome gegebenenfalls mit einem oder mehreren der oben genannten Reste weiter substituiert ist/sind und wobei der Kohlenwasserstoff gesättigt, ungesättigt oder ein aromatischer Kohlenwasserstoff ist. Hinsichtlich der Reste R1–R10 gelten dieselben Vorzugsvarianten wie bei R1–R4 und R7–R14 der allgemeinen Formel I. Preferred representatives of the general structure I are N-heterocyclic or pure phenanthrenequinones of the general formula Ia,

in which
Y1, 2 and Y3, 4 have the meaning of Y1, 2 mentioned for the general formula I and Y3 and Y4 can additionally represent a carboxy (= O) group and wherein
X1-X4 and X7-X10 are the same or different and each independently is a nitrogen atom or a carbon atom, wherein the carbon atoms in X1-X10 bear radicals R1-10, which are the same or different and are each independently selected from the group of Hydrogen halo, cyano, nitro, nitroso, sulfamide carboxy, C1-C20 carbalkoxy, C1-C20 alkyl sulfo, = O, sulfohalogen, halocarbonyl, carbamoyl, formyl, amidine formyl, C 1 -C 6 -alkylsulfanyl and C 1 -C 20 -alkylsulfonyl radical and C 1 -C 20 -hydrocarbon wherein one or more or all of the carbon atoms are optionally further substituted by one or more of the radicals mentioned above and wherein the hydrocarbon is saturated, unsaturated or is an aromatic hydrocarbon. With regard to the radicals R 1 -R 10, the same preferred variants apply as in R 1 -R 4 and R 7 -R 14 of the general formula I.

The representatives of the general formula Ia favor the presence of two nitrogen atoms which are preferably located at the positions X1 and X10 or X4 and X7, the remaining X groups in each case being carbon.

Preferred Structures 1a

wobei
Y1, 2 die zur allgemeinen Formel I genannte Bedeutung haben und
wobei entweder X1–4 und X7–10 (sechs Stickstoffatome) oder X2, X4, X9 und X7 (vier Stickstoffatome) oder X5 und X6 (zwei Stickstoffatome) oder X1–10 (acht Stickstoffatome) oder X4 und X7 (zwei Stickstoffatome) oder X2 und X9 (zwei Stickstoffatome) Stickstoffatome sind, oder mindestens ein X ein Stickstoffatom ist und eine unsymmetrische Substitution durch Stickstoffatome an X-Positionen vorliegt,
wobei alle verbleibenden X-Gruppen Kohlenstoffatome sind, wobei die Kohlenstoffatome bei X1–X10 Reste R1–10 tragen, welche gleich oder verschieden sind und jeweils unabhängig voneinander ausgewählt sind aus der Gruppe von Wasserstoff Halogen-, Cyano-, Nitro-, Nitroso-, Sulfamid- Carboxy-, C1-C20-Carbalkoxy-, C1-C20-Alkylsulfo-, =O, Sulfohalogen-, Halogencarbonyl-, Carbamoyl-, Formyl-, Amidinformyl-, C1-C6-Alkylsulfanyl-und C1-C20-Alkylsulfonyl-Rest und C1-C20-Kohlenwasserstoff, wobei eines oder mehrere oder alle Kohlenstoffatome gegebenenfalls mit einem oder mehreren der oben genannten Reste weiter substituiert ist/sind und wobei der Kohlenwasserstoff gesättigt, ungesättigt oder ein aromatischer Kohlenwasserstoff ist. Hinsichtlich der Reste R1–R10 gelten dieselben Vorzugsvarianten wie bei R1–R4 und R7–R14 der allgemeinen Formel I. Further preferred representatives of the general structure I are compounds of the general formula Ib

in which
Y1, 2 have the meaning given to general formula I and
where either X1-4 and X7-10 (six nitrogen atoms) or X2, X4, X9 and X7 (four nitrogen atoms) or X5 and X6 (two nitrogen atoms) or X1-10 (eight nitrogen atoms) or X4 and X7 (two nitrogen atoms) or X2 and X9 (two nitrogen atoms) are nitrogen atoms, or at least one X is a nitrogen atom and there is an asymmetric substitution by nitrogen atoms at X positions,
wherein all remaining X groups are carbon atoms, the carbon atoms in X1-X10 bear radicals R1-10 which are identical or different and are each independently selected from the group of hydrogen, halogen, cyano, nitro, nitroso, Sulfamide-carboxy, C1-C20-carbalkoxy, C1-C20-alkylsulfo, = O, sulfohalogen, halocarbonyl, carbamoyl, formyl, amidinoformyl, C1-C6-alkylsulfanyl and C1-C20-alkylsulfonyl A radical and C 1 -C 20 -hydrocarbon wherein one or more or all carbon atoms are optionally further substituted by one or more of the abovementioned radicals and where the hydrocarbon is saturated, unsaturated or an aromatic hydrocarbon. With regard to the radicals R 1 -R 10, the same preferred variants apply as in R 1 -R 4 and R 7 -R 14 of the general formula I.

When X1, X4, X7 and X10 (four nitrogen atoms) or X1 and X10 (two nitrogen atoms) or no nitrogen atom are present in the formula 1b, only the following end groups Y1 and / or Y2 may be the same as C (CN) ₂ , = C ( CN) CF _3, = N (CN) = C ₆ H ₄ = C (CN) _2, = C ₆ F ₄ = C (CN) _2, = C ₅ H ₃ N = C (CN) _{2 was} used.

By "asymmetric substitution by nitrogen atoms at X positions" is meant that there is no symmetry with respect to the mirror plane perpendicular to X5 and X6 and between X1 and X10.

Preferred Structures 1b

wobei
Y1 und Y2 die für die allgemeine Formel I genannte Bedeutung haben und wobei
X1–X14 gleich oder verschieden sind und jeweils unabhängig voneinander ein Stickstoffatom oder ein Kohlenstoffatom sind,
wobei die Kohlenstoffatome bei X1–X14 Reste R1–R14 tragen, welche gleich oder verschieden sind und jeweils unabhängig voneinander ausgewählt sind aus der gleichen Gruppe wie R1–R4 und R7–R14 zur allgemeinen Formel I. Hinsichtlich der Reste R1–R14 gelten dieselben Vorzugsvarianten wie bei R1–R4 und R7–R14 der allgemeinen Formel I. Preferred representatives of the general structure I are likewise ortho-fused quinoid N-heterocyclic compounds of the general formula Ic,

in which
Y1 and Y2 have the meaning given for the general formula I and wherein
X1-X14 are the same or different and each independently is a nitrogen atom or a carbon atom,
wherein the carbon atoms in X1-X14 carry radicals R1-R14 which are identical or different and are each independently selected from the same group as R1-R4 and R7-R14 to general formula I. With regard to the radicals R1-R14, the same preferred variants apply as in R1-R4 and R7-R14 of general formula I.

In these representatives of general formula Ic, the presence of two, four or six nitrogen atoms is preferred, with two nitrogen atoms preferably being found at positions X1 and X10 or X11 and X14 or X4 and X7. In the case of four nitrogen atoms, these are preferably located at the positions X1, X4, X7 and X10, or X1, X10, X11 and X14, or X4, X7, X11 and X14. The six nitrogen atom constellation is preferably based on their positioning on X1, X4, X7, X10, X11 and X14. In all variants, the remaining X groups are each carbon.

In the case of two nitrogen atoms at the positions X11 and X13 in the general formula Ic, it is particularly preferred that the remaining X groups are each carbon, wherein X12 and X13 are each -C≡N radicals.

Preferred Structures 1c

wobei
Y1, 2 die zur allgemeinen Formel I genannte Bedeutung haben und wobei
X1–X10 gleich oder verschieden sind und jeweils unabhängig voneinander ein Stickstoffatom oder ein Kohlenstoffatom sind,
wobei die Kohlenstoffatome bei X1–X10 Reste R1–R10 tragen, welche gleich oder verschieden sind und jeweils unabhängig voneinander ausgewählt sind aus der gleichen Gruppe wie R1–R4 und R7–R14 zur allgemeinen Formel I. Hinsichtlich der Reste R1–R10 gelten dieselben Vorzugsvarianten wie bei R1–R4 und R7–R14 der allgemeinen Formel I. In dieser allgemeinen Formel Id stellen bevorzugt zwei, vier oder sechs X-Gruppen Stickstoff dar, wobei bei zwei Stickstoffatomen deren Präsenz an den Positionen X1 und X10 bevorzugt ist und bei vier Stickstoffatomen diese sich bevorzugt an den Positionen X1, X4, X7 und X10 finden. Bei diesen beiden Varianten stehen die verbleibenden X-Gruppen jeweils für Kohlenstoff. Im Falle von sechs Stickstoffatomen sind alle X (1, 2, 4, 7, 9, 10) Stickstoff. Further preferred representatives of the general formula I are quinoid bipyridyl, bipyrimidine or bitriazine derivatives of the general formula Id,

in which
Y1, 2 have the meaning given to general formula I and wherein
X1-X10 are the same or different and each independently is a nitrogen atom or a carbon atom,
where the carbon atoms in X1-X10 carry radicals R1-R10 which are identical or different and are each independently selected from the same group as R1-R4 and R7-R14 to general formula I. With regard to the radicals R1-R10, the same preferred variants apply as in the case of R 1 -R 4 and R 7 -R 14 of the general formula I. In this general formula Id, two, four or six X groups preferably represent nitrogen, with two nitrogen atoms whose presence at the positions X 1 and X 10 being preferred and four nitrogen atoms being preferred these are preferably located at the positions X1, X4, X7 and X10. In both of these variants, the remaining X groups are each carbon. In the case of six nitrogen atoms, all X (1, 2, 4, 7, 9, 10) are nitrogen.

Preferred structures 1d

The compounds of general formula I and in particular the compounds according to Ia-Id have a higher reduction potential and / or better thermal stability and / or diffusion stability. Due to the higher evaporation temperature or less volatiles under the same conditions, the production processes can be better controlled and carried out with less effort and reproducible, with the provision of these compounds as dopants these ensure in the respective components with low diffusion coefficients, the same time constant component structures, allow a sufficient electrical conductivity of the organic semiconducting matrix with favorable electron affinity of the dopants. Furthermore, the dopants can be used to improve the charge carrier injection of contacts into the doped layer. The doped organic semiconductor material or the resulting electronic component has improved long-term stability due to the compounds used according to the invention. This concerns, for example, a reduction of the dopant concentration with time. Further this relates to the stability of the doped layer, which is arranged adjacent to undoped layers of an electro-optical component, so that electro-optical components with increased long-term stability of the electro-optical properties such as luminous efficacy at a given wavelength, efficiency of a solar cell or the like result.

The vapor deposition rate of the substrate with the compounds according to the invention can be determined, for example, using a quartz thickness monitor, as is commonly used, for example, in the production of OLEDs. In particular, the ratio of vapor deposition rates of matrix materials and dopants may be measured by independent measurements thereof using two separate quartz thickness monitors to adjust the doping ratio.

It is understood that the compounds used in the invention are preferably such that they evaporate more or less or virtually undecomposed.

Targeted precursors are also usable as a dopant source, which release the compounds used according to the invention, such as acid addition salts, for example a volatile or nonvolatile inorganic or organic acid, or charge transfer complexes thereof, wherein the acids or electron donors preferably not or only slightly volatile or the charge transfer complex itself acts as a dopant.

Irrespective of whether the dopant is a quinoidal N-heterocycle, quinoidal N-heteropolycycle or a quinoidal phenanthrene derivative, it is preferably selected such that it can be used under given conditions such as, in particular, doping concentration (molar ratio of dopant: matrix, layer thickness, current intensity) for a given matrix material ( For example, zinc phthalocyanine or another matrix material mentioned below) generates as high or preferably a higher conductivity than F4TCNQ, for example, a conductivity (S / cm) greater than or equal to 1.1 times, 1.2 times or greater / equal to 1.5 times or twice that of F4TCNQ as dopant.

Preferably, the dopant used in the invention is selected such that the doped with this semiconducting organic matrix material after a change in temperature of 100 ° C to room temperature (20 ° C) still ≥ 20%, preferably ≥ 30%, more preferably ≥ 50% or 60% of Conductivity (S / cm) of the value at 100 ° C.

The synthesis of the inventive quinoid N-heterocycles, quinoid N-Heteropolyzyklen and quinoid phenanthrene derivatives of general formula I can be done in various ways, one of which is exemplified in Scheme 1 below.

wobei die X-Reste und die Reste Y1 und Y2 die zur allgemeinen Formel I genannte Bedeutung haben, basiert auf der Umsetzung von Verbindungen der allgemeinen Formel V,

wobei die X-Reste die zur allgemeinen Formel I genannte Bedeutung haben und mindestens zwei der X-Reste Stickstoff bedeuten, zu N-Oxiden und anschließende Umsetzung mit einer Verbindung der Formel (CF₃)₂C=Y_1,2, wobei Y1 oder Y2 die zur allgemeinen Formel I genannte Bedeutung haben. Die Umsetzung zum N-Oxid erfolgt vorzugsweise mit HOF und Acetonitril. The novel process according to the invention for the preparation of quinoid N-heterocycles, quinoid N-heteropolycycles and quinoid phenanthrene derivatives of the general formula I

where the X radicals and the radicals Y1 and Y2 have the meaning given to general formula I, is based on the reaction of compounds of general formula V,

wherein the X radicals have the meaning given to general formula I and at least two of the X radicals represent nitrogen, to N-oxides and subsequent reaction with a compound of formula (CF ₃ ) ₂ C = Y _1.2 , wherein Y1 or Y2 have the meaning given to general formula I. The conversion to the N-oxide is preferably carried out with HOF and acetonitrile.

The new synthesis variant is shown by way of example in Scheme 2, wherein the synthesis per se is not limited to the substituents shown there.

Schema 2

Scheme 2

Schema 3 Highly conductive CT complexes can be prepared from electron-rich compounds, metal salts, such as amines, in particular from aromatic and heteroaromatic amines, pyridines or tetrathiofulvalenes and the quinone derivatives according to the invention, as shown by way of example in Scheme 4 below.

Scheme 3

The quinonoid N-heterocycles, quinoid N-heteropolycycles, or quinoid phenanthrene derivatives, or anionic radical salts or CT complexes, according to the invention, find use as organic dopants for doping an organic semiconductive matrix material to alter its electrical properties. They are also used as blocking layer, as charge injection layer or as organic semiconductor. Further uses are as electrode material or electric n-conductors in OLEDs, solar cells, field effect transistors, data storage, batteries, fuel cells, magnets or in electronic and optoelectronic components. Another application relates to the electrolyte in batteries, in dye-sensitized solar cells (DSSC) or in capacitors. Also included is use as a switch and memory, as well as use in organic magnets.

matrix materials

The present invention describes suitable dopants for organic semiconductive materials such as hole transport materials HTM, which are commonly used in OLEDs or organic solar cells. These semiconductive materials are preferably intrinsically hole-conducting. For dopants according to the invention, the following may apply.

The matrix material may be partially (> 50 or> 75 wt%) or substantially (> 90 wt% or> 95 wt%) or entirely composed of a metal phthalocyanine complex, a porphyrin complex, especially a metal porphyrin complex , an oligothiophene, oligophenyl, oligophenylenevinylene or oligofluorene compound, wherein the oligomer preferably comprises 2-500 or more, preferably 2-100 or 2-50 or 2-10 monomeric units. Optionally, the oligomer may also comprise> 4,> 6 or> 10 or more monomeric units, in particular also for the ranges indicated above, ie for example 4 or 6-10 monomeric units, 6 or 10-100 monomeric units or 10-500 monomeric units , The monomers or oligomers may be substituted or unsubstituted, wherein block or copolymers may be present from said oligomers, a compound having a triarylamine unit or a spiro-bifluorene compound. The matrix materials mentioned can also be present in combination with one another, if appropriate also in combination with other matrix materials. The matrix materials may have electron donating substituents such as alkyl or alkoxy moieties which have reduced ionization energy or reduce the ionization energy of the matrix material.

The metal phthalocyanine complexes or porphyrin complexes used as the matrix material may have a main group metal atom or a subgroup metal atom. The metal atom may each be 4-, 5- or 6-fold coordinated, for example in the form of oxo (Me = O), dioxo (O = Me = O), imine, diimine, hydroxo, dihydroxo, Amino or diamino complexes, without being limited thereto. The phthalocyanine complex or porphyrin complex may each be partially hydrogenated, but preferably the mesomeric ring system is not disturbed. The phthalocyanine complexes may contain as central atom, for example, magnesium, zinc, tin, silicon, iron, nickel, cobalt, magnesium, copper, titanyl or vanadyl (= VO). The same or different metal atoms or oxometal atoms may be present in the case of porphyrin complexes.

In particular, such dopable hole transport materials may include HTM arylated benzidines, for example N, N'-perarylated benzidines or other diamines such as TPD (where one, several or all of the aryl groups may have aromatic heteroatoms), suitable arylated starburst compounds such as N, N ', N "- perarylated starburst compounds, such as the compound TDATA (wherein one, several or all of the aryl groups may have aromatic heteroatoms). The aryl groups may specifically include phenyl, naphthyl, pyridine, quinoline, isoquinoline, peridazine, pyrimidine, pyrazine, pyrazole, imidazole, oxazole, furan, pyrrole, indole, or the like, for each of the above-mentioned compounds. The phenyl groups of the respective compounds may be partially or completely replaced by thiophene groups.

Preferably, the matrix material used consists entirely of a metal phthalocyanine complex, a porphyrin complex, a compound with triarylamine units, a spiro-bifluorene compound or oligo-thiophenes and oligo-selenophenes.

It is understood that suitable other organic matrix materials, in particular hole-conducting materials can be used which have semiconducting properties.

endowment

The doping may in particular be such that the molar ratio of matrix molecule to dopant or, in the case of oligomeric matrix materials, the ratio of matrix monomer number to dopant 1: 100000, preferably 1: 1 to 1: 10000, particularly preferably 1: 5 to 1: 1000, for example 1:10 to 1: 100, for example, about 1:50 to 1: 100 or even 1:25 to 1:50.

Evaporation of the dopants

• a) Mischverdampfung im Vakuum mit einer Quelle für HTM und einer für den p-Dotand
• b) Sequentielles Deponieren von HTM und p-Dotand mit anschliessender Eindiffusion des Dotanden durch thermische Behandlung
• c) Dotierung einer HTM-Schicht durch eine Lösung von Dotanden mit anschliessendem Verdampfen des Lösungsmittels durch thermische Behandlung
• d) Oberflächendotierung einer HTM-Schicht durch eine oberflächlich aufgebrachte Schicht von Dotanden

The doping of the respective matrix material (here preferably indicated as hole-conducting matrix material HTM) with the dopants to be used according to the invention can be produced by one or a combination of the following processes:

• a) Mixed evaporation in vacuo with a source of HTM and one for the p-dopant
• b) Sequential deposition of HTM and p-dopant with subsequent diffusion of the dopant by thermal treatment
• c) doping of an HTM layer by a solution of dopants with subsequent evaporation of the solvent by thermal treatment
• d) Surface doping of an HTM layer by a superficially applied layer of dopants

Other common methods to obtain a doped layer are spin-coating, injection printing or organic vapor phase deposition (OVPD) or evaporation in a roll to roll process.

The doping can be carried out in such a way that the dopant is evaporated out of a precursor compound which releases the dopant on heating and / or irradiation. The irradiation can be effected by means of electromagnetic radiation, in particular visible light, UV light or IR light, for example, in each case laser light, or else by other types of radiation. The irradiation can essentially provide the heat necessary for the evaporation, it can also be irradiated deliberately into specific bands of the compounds or precursors or compound complexes to be vaporized, such as charge-transfer complexes, in order to evaporate the compounds, for example by converting them into excited states to facilitate by dissociation of the complexes. It is understood that the evaporation conditions described below are directed to those without irradiation and for comparison purposes uniform evaporation conditions are used.

• a) Gemische oder stöchiometrische oder mischkristalline Verbindungen aus dem Dotand und einer inerten, nichtflüchtigen Substanz, z.B. einem Polymer, Molsieb, Aluminiumoxid, Kieselgel, Oligomeren oder einer anderen organischen oder anorganischen Substanz mit hoher Verdampfungstemperatur, wobei der Dotand vorwiegend durch van-der-Waals Kräfte und/oder Wasserstoffbrückenbindung an dieser Substanz gebunden ist.
• b) Gemisch oder stöchiometrische oder mischkristalline Verbindung aus dem Dotand und einer mehr oder weniger Elektronendonor-artigen, nicht flüchtigen Verbindung, wobei ein mehr oder weniger vollständiger Ladungstransfer zwischen dem Dotanden und der Verbindung auftritt, wie in Charge-Transfer-Komplexen mit mehr oder weniger elektronenreichen Polyaromaten oder Heteroaromaten oder einer anderen organischen oder anorganischen Substanz mit hoher Verdampfungstemperatur.
• c) Gemisch oder stöchiometrische oder mischkristalline Verbindung aus dem Dotand und einer Substanz, welche zusammen mit dem Dotand verdampft und eine gleiche oder höhere Ionisierungsenergie aufweist wie die zu dotierende Substanz HT, so dass die Substanz in dem organischen Matrixmaterial keine Haftstelle für Löcher bildet. Hierbei kann die Substanz erfindungsgemäß auch mit dem Matrixmaterial identisch sein, beispielsweise ein Metallphtalocyanin oder Benzidin-Derivat darstellen. Weitere geeignete flüchtige Co-Substanzen, wie Hydrochinone, 1,4-Phenylendiamine oder 1-Amino-4-hydroxybenze oder sonstige Verbindungen bilden Chinhydrone oder andere Charge-Transfer-Komplexe.

As precursor compounds can be used, for example:

• a) mixtures or stoichiometric or mixed crystalline compounds of the dopant and an inert, non-volatile substance, such as a polymer, molecular sieve, alumina, silica gel, oligomers or other organic or inorganic substance having a high evaporation temperature, wherein the dopant predominantly by van der Waals Forces and / or hydrogen bonding is bound to this substance.
• b) Mixture or stoichiometric or mixed crystalline compound of the dopant and a more or less electron donor-like, non-volatile compound, wherein a more or less complete charge transfer between the dopant and the compound occurs, as in charge-transfer complexes with more or less electron-rich polyaromatic or heteroaromatic or other organic or inorganic substance with high evaporation temperature.
• c) mixture or stoichiometric or mixed crystalline compound of the dopant and a substance which evaporates together with the dopant and has an ionization energy equal to or higher than the substance to be doped HT, so that the substance in the organic matrix material does not form a trap for holes. In this case, the substance according to the invention may also be identical to the matrix material, for example a metal phthalocyanine or benzidine derivative. Other suitable volatile co-substances, such as hydroquinones, 1,4-phenylenediamines or 1-amino-4-hydroxybenze or other compounds form quinhydrones or other charge-transfer complexes.

Electronic Components

Using the organic compounds according to the invention for producing doped organic semiconducting materials, which may be arranged in particular in the form of layers or electrical conduction paths, a multiplicity of electronic components or devices containing them can be produced. In particular, the dopants of the invention may be used to make organic light emitting diodes (OLED), organic solar cells (OSC), dye sensitized solar cells (DSSC's), organic diodes, especially those having a high r.f. ratio, such as 10 ³ -10 ⁷ , preferably 10 ⁴ -10 ⁷ or 10 ⁵ -10 ⁷ or OFET's), batteries, sensors, fuel cells, data memories, as organic conductors, as electrode materials or in capacitors. The electrical dopants according to the invention can be used to improve the conductivity of the doped layers and / or to improve the charge carrier injection of contacts into the doped layer. Particularly in the case of OLEDs, the component may have a pin structure or an inverse structure, without being limited thereto. However, the use of the dopants according to the invention is not limited to the abovementioned advantageous variants.

The invention will be explained in more detail in some embodiments.

Examples 1

Preparation of 5,5'-bis (dicyanomethyl) 2,2'-bipyridyl

0.01 mol of malononitrile dissolved in THF is slowly added dropwise under protective gas and ice cooling to a suspension of 0.012 mol of NaH and 100 ml of THF and stirred for a further 20 min at room temperature after completion. Subsequently, 0.005 mol of 5,5'-dibromo-2,2'-bipyridyl, 0.001 mol of PdCl ₂ and 0.001 mol of phosphorous triphenyl are added and heated under reflux for 12 h. After appropriate workup 94% crude product was obtained.

Preparation of tetracyano-2,2'-bipyridyl-5,5'-quinonedimethanes

1 mmol of 5,5'-bis (dicyanomethyl) 2,2'-bipyridyl are mixed in aqueous solution with bromine water, filtered off with suction in a suitable solvent, such as methylene chloride dried with MgSO ₄ , concentrated and filtered with suction. Yield: 70%

Example 2

Preparation of 3,8-dibromopyrazino [2,3-f] [1,10] phenanthroline-2,3-dicarbonitriles

A mixture of 200 ml of 1-chlorobutane, 5 g of pyrazino [2,3-f] [1,10] phenanthroline-2,3-dicarbonitrile, 12.3 g of sulfur monochloride, 7.1 g of pyridine and 14 g of bromine is heated at reflux for 12 h. After cooling, the resulting solid is taken up in dilute excess sodium hydroxide solution and 100 ml of chloroform. The organic phase is separated and separated on a short silica gel column. The yield is 65%.

Preparation of 3,8-bis (dicyanomethyl) pyrazino [2,3-f] [1,10] phenanthroline-2,3-dicarbonitriles

11 mmol of malononitrile in 100 ml of THF are slowly added under cooling and inert gas with 12 mmol of NaH. After completion of the gas evolution is stirred for a further 30 min at room temperature. 5 mmol of 3,8-dibromopyrazino [2,3-f] [1,10] phenanthroline-2,3-dicarbonitrile and 0.14 mmol of P (Ph) ₃ and 0.14 mmol of PdCl _{2 are} added to this suspension and the mixture is refluxed for 8 hours , After acidic work-up by means of dilute hydrochloric acid 82% product were obtained.

Preparation of tetracyano-pyrazino [2,3-f] [1,10] phenanthroline-3,8-quinonedimethanes-2,3-dicarbonitriles

To a weakly acidic aqueous suspension of 3,8-bis (dicyanomethyl) pyrazino [2,3-f] [1,10] phenanthroline-2,3-dicarbonitrile (1.3 g in 100 ml) is added as much bromine water to the red color of the radical anion disappears and a yellow / brown solid has formed, which is rapidly sucked off and taken up in methylene chloride. The solution is dried with MgSO ₄ , filtered and concentrated. The yield of the precipitated crystals is 78%.

Example 3

Preparation of 3,8-bis (dicyanomethyl) 1,10-phenanthroline

0.01 mol of malononitrile dissolved in THF is slowly added dropwise under protective gas and ice cooling to a suspension of 0.012 mol of NaH and 100 ml of THF and stirred for a further 20 min at room temperature after completion. Subsequently, 0.005 mol of 3,8-dibromo-1,10-phenanthroline, 0.001 mol of PdCl ₂ and 0.001 mol of phosphorotriphenyl and 0.001 mol of NaH are added and the mixture is heated under reflux for 12 h. After appropriate aqueous work-up, 90% of product was obtained.

Preparation of tetracyano-1,10-phenanthrolinquinone-3,8-imethanes

1 mmol of 3,8-bis (dicyanomethyl) -1,10-phenanthroline are treated in aqueous solution with bromine water for a few minutes, filtered off, washed with water and dried in vacuo. After sublimation, 78% pure product was obtained.

Example 4

3,8-bis (pentafluorophenyl) -1,10-phenanthroline

0.5 mmol 3,8-dibromo-1,10-phenanthroline, 212 mg (1.0 mmol pentafluorophenyl boronic acid ester, 81.5 mg (0.08 mmol) tetrakis (triphenyl) palladium, 460 mg (2.0 mmol) Ag 2 O, 1.7 g of K3PO4 are intensively stirred under protective gas in 10 ml of DMF at 90 ° C. for 6 hours After cooling, the reaction mixture is poured into Wasswer and extracted with methylene chloride, dried over MgSO4 and concentrated to dryness in vacuo and recrystallized from a suitable solvent. The yield was 81%.

4 ', 4' '- dicyanomethyl-3,8-bis (pentafluorophenyl) -1,10-phenanthroline

0.01 mol of malononitrile dissolved in THF is slowly added dropwise under protective gas and ice cooling to a suspension of 0.012 mol of NaH and 100 ml of THF and stirred for a further 20 min at room temperature after completion. Then add 0.005 mol of 3,8-bis (pentafluorophenyl) -1,10-phenanthroline, stirred vigorously and heated at reflux for 8 h. After cooling, the mixture is concentrated in vacuo, cooled, filtered off and recrystallized. The white crystalline product was obtained in 98% yield.

Tetracyano-bis (tetrafluorophenyl) -1,10-phenanthroline-3,8-quinones 7 ', 7' '- dimethanes

1 mmol of 4 ', 4' '- dicyanomethyl-3,8-bis (pentafluorophenyl) -1,10-phenanthroline is stirred in 10 ml of a mixture of 40% sulfuric acid and chromium (IV) oxide for 10 min at room temperature, in Water is added and sucked off. The product was dried in vacuo and sublimed. Yield: 63%

The compounds to be used according to the invention, in particular the compounds of the above-described class of the quinoid N-heterocycles, quinoid N-heteropolycycles and quinoid phenanthrene derivatives are used in the manner described below as dopants for various hole conductors, which in turn for the construction of certain microelectronic or optoelectronic Components, such as an OLED used. In this case, the dopants can be simultaneously evaporated side by side with the hole transport materials of the matrix under high vacuum (about 2 × 10 ^-4 Pa) at elevated temperatures. A typical substrate evaporation rate for the matrix material is 0.2 nm / s (density about 1.5 g / cm ³ ). The evaporation rates for the dopants can vary between 0.001 and 0.5 nm / s with the same assumed density, in each case corresponding to the desired doping ratio.

Current measurements were carried out over a 1 mm long and about 0.5 mm wide current path of the doped HT material at 1V. Under these conditions, ZnPc conducts virtually no electric current.

conductivity measurements

ZnPc / tetracyano-2,2'-bipyridyl-4,4'-quinonedimethane 5% dopant: 10 ^-3 S / cm

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 1990847 A1 [0003]
• US 6908783 B1 [0003]

Cited non-patent literature

• M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (22), 3202-3204 (1998) [0002]
• J. Blochwitz, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (6), 729-731 (1998) [0002]
• Gao et al. in Chem. Commun., 2008, 117-119 [0003]

Claims (12)

Chinoids N-heterocycles, quinoid N-Heteropolyzyklen and quinoid phenanthrene derivatives of general formula I.

wherein Y1 and Y2 are the same or different and are each independently C for a = NCN, = (CN) ₂ -, = C (CF ₃₎ R, = C (C ₆ F _{5) 2} -, = C (heteroaryl ) ₂ -, = C (CF ₃ ) ₂ -, = C (CN) R-radical or = C (CN) (CF ₃ ) radical, wherein the radicals R are selected from the group of hydrogen, halogen, cyano , Nitro, nitroso, sulfamide, carboxy, C1-C20-carbalkoxy, C1-C20-alkylsulfo, sulfohalogen, sulfonic acid, electron-poor aromatic or heteroaromatic, halocarbonyl, carbamoyl, formyl, amidine-formyl C 1 -C 6 -alkylsulfanyl and C 1 -C 20 -alkylsulfonyl radical and C 1 -C 20 -hydrocarbon wherein one or more or all of the carbon atoms are optionally further substituted by one or more of the radicals mentioned above, and wherein the hydrocarbon is saturated, unsaturated or is an aromatic hydrocarbon, or represents a group of the general formula II,

wherein Xa-Xe are the same or different and each independently is a nitrogen atom or a carbon atom, wherein the carbon atoms carry radicals Ra-e which are the same or different and are each independently selected from the same group as R and wherein X1-X4 and X7-X14 are the same or different and each independently is a nitrogen atom or a carbon atom, wherein the carbon atoms in X1-X4 and X7-X14 bear R1-R4 and R7-R14 which are the same or different and are each independently selected are selected from the group of hydrogen, halogen, cyano, nitro, nitroso, sulfamide, carboxy, C1-C20-carbalkoxy, C1-C20-alkylsulfo, = O, sulfohalogen, halocarbonyl, carbamoyl, Formyl, amidinoformyl, C 1 -C 6 alkylsulfanyl and C 1 -C 20 alkylsulfonyl radicals and C 1 -C 20 hydrocarbons, wherein one or more or all of the carbon atoms are optionally substituted with one or more of the above g and wherein the hydrocarbon is saturated, unsaturated or an aromatic hydrocarbon and wherein X5 and X6 are the same or different and are each independently a nitrogen atom or a carbon atom, wherein the carbon atoms carry radicals R5, R6, which are identical or are different and are each independently selected from the same group as R1-R4 and R7-R14, or X5, X6 are each a C = Y ³ radical (X5), C = Y ⁴ radical (X6), wherein Y3, 4 are each independently selected from the same groups as Y1, 2, and in this case X11-X14 is omitted or X5, X6 and X11-X14 are eliminated. Chinoids N-heterocycles, quinoid N-Heteropolyzyklen and quinoid phenanthrene derivatives according to claim 1, characterized in that they are N-heterocyclic or pure phenanthrenequinones of the general formula Ia,

where Y 1, 2 and Y 3, 4 have the meaning of Y 1, 2 mentioned in claim 1 and Y 3 and Y 3 additionally additionally represent an = O radical where X 1 -X 10 are the same or different and are each independently a nitrogen atom or a carbon atom, wherein the carbon atoms in X1-X10 carry radicals R1-10, which are identical or different and are each independently selected from the group of hydrogen, halogen, cyano, nitro, nitroso, sulfamide, carboxy, C1-C20- Carbalkoxy, C1-C20 alkyl sulfo, = O, sulfohalogen, halocarbonyl, carbamoyl, formyl, amidinoformyl, C1-C6 alkylsulfanyl and C1-C20 alkylsulfonyl radical and C1-C20 hydrocarbon, wherein one or more or all of the carbon atoms are optionally further substituted by one or more of the abovementioned radicals, and wherein the hydrocarbon is saturated, unsaturated or an aromatic hydrocarbon. Chinoids N-heterocycles, quinoid N-heteropolycycles and quinoid phenanthrene derivatives according to claim 1, characterized in that they are N-heterocyclic of the general formula Ib,

wherein Y1, 2 have the meaning given in claim 1 and wherein X1-4 and X7-10, or X4 and X6, or X4 and X7 or X2 and X9 are nitrogen atoms or at least one X is nitrogen and there is an unsymmetrical substitution by nitrogen atoms, wherein the remaining X groups are carbon atoms, the carbon atoms in X1-X10 bear radicals R1-10 which are identical or different and are each independently selected from the group of hydrogen, halogen, cyano, nitro, nitroso, Sulfamide-carboxy, C1-C20-carbalkoxy, C1-C20-alkylsulfo, = O, sulfohalogen, halocarbonyl, carbamoyl, formyl, amidinoformyl, C1-C6-alkylsulfanyl and C1-C20-alkylsulfonyl A radical and C 1 -C 20 -hydrocarbon wherein one or more or all carbon atoms are optionally further substituted by one or more of the abovementioned radicals and where the hydrocarbon is saturated, unsaturated or an aromatic hydrocarbon. Chinoids N-heterocycles, quinoid N-heteropolycycles and quinoid phenanthrene derivatives according to claim 1, characterized in that they are ortho-fused quinoid N-heterocyclic compounds of general formula Ic,

wherein Y1 and Y2 have the meaning given in claim 1 and wherein X1-X14 are identical or different and are each independently a nitrogen atom or a carbon atom, wherein the carbon atoms in X1-X14 carry radicals R1-R14 which are identical or different and are each independently selected from the same group as R1-R4 and R7-R14 in claim 1. Chinoids N-heterocycles, quinoid N-Heteropolyzyklen and quinoid phenanthrene derivatives according to claim 1 or 4, characterized in that in the general formula Ic X1 and X10 or X11 and X14 or X4 and X7 or X1, X4, X7 and X10, or X1, X10, X11 and X14, or X4, X7, X11 and X14, or X1, X4, X7, X10, X11 and X14 denote nitrogen, wherein the remaining X groups are each carbon. Chinoids N-heterocycles, quinoid N-heteropolycycles and quinoid phenanthrene derivatives according to any one of claims 1, 4 or 5, wherein X11 and X14 are nitrogen and the remaining X groups are each carbon, wherein X12 and X13 are each -C≡N radicals are. Chinoids N-heterocycles, quinoid N-Heteropolyzyklen and quinoid phenanthrene derivatives according to claim 1, characterized in that they are quinoid bipyridyl, bipyrimidine or bitriazine derivatives of the general formula Id,

wherein Y1, Z2 have the meaning given in claim 1 and wherein X1-X10 are the same or different and are each independently a nitrogen atom or a carbon atom, wherein the carbon atoms in X1-X10 radicals R1-R10 carry, which are identical or different and are each independently selected from the same group as R1-R4 and R7-R14 in claim 1. Chinoids N-heterocycles, quinoid N-heteropolycycles and quinoid phenanthrene derivatives according to claim 1 or 6, characterized in that in the general formula Id X1 and X10 or X1, X4, X7 and X10 or all X (1, 2, 4, 7, 9, 10) nitrogen, wherein the remaining X groups are each carbon. Use of inventive, pure, quinoidal N-heterocycles, pure and quinoidal N-Heteropolyzyklen and pure and quinoidal phenanthrene derivatives or as any mixture with any other substances in optoelectronic or electronic components, in particular in organic light emitting diodes (OLED`s), in organic diodes, in organic field effect transistors (OFETs) in fuel cells, in capacitors (so-called super capacitors,) in electrochromic displays, in organic solar cells (OSC, DSSC), in batteries and accumulators, in energy storage systems, in electronic or optoelectronic or magnetic data storage elements, in magnets, in components for photocatalytic water splitting preferably as electrical p-dopants, in organic CMOS (hybrid CMOS), RFID's (Radio Frequency Identification Device), in sensors, as an electron transport material, as a hole blocker, as a charge injection layer, as a host material for emitters, as an electrode material, as an electrolyte, as an absorber, as an emitter itself. Use of a pure, quinoid N-heterocycle according to the invention or as any desired mixture with any other substance in electronic or optoelectronic components, preferably in OLEDs, OSCs, DSSCs, batteries or accumulators as well as capacitors as p-dopant, organic semiconductor materials (ETM), electrode materials, Charge injection layers or hole blocker layers, in organic CMOS (Hybrid CMOS), RFID's (Radio Frequency Identification Device), in sensors. Use of a pure, quinoid N-heteropolycycles according to the invention or as an arbitrary mixture with any other substance in electronic or optoelectronic components, preferably in OLEDs, OSCs, DSSCs, batteries or rechargeable batteries as well as capacitors as p-dopant, organic semiconductor materials (ETM), electrode materials, Charge injection layers or hole blocker layers, in organic CMOS (Hybrid CMOS), RFID's (Radio Frequency Identification Device), in sensors. Use of a pure, quinoid Phenanthrenderivatse invention or as any mixture with any other substance in electronic or optoelectronic devices preferably in OLEDs, OSC's, DSSC's, batteries or rechargeable batteries and capacitors as p-dopant, organic semiconductor materials (ETM), electrode materials, charge injection layers or Hole blocker layers in organic CMOS (Hybrid CMOS), RFID's (Radio Frequency Identification Device), in sensors.