DE102006011270A1 - New perylene bisimide radical anion as salt, useful e.g. as a dye in magnetic materials and electronic building elements, as materials for magnetic or electro magnetic shieldings, as magnetic materials for signal recorders - Google Patents

Abstract

Perylene bisimide radical anion (A) as salt, preferably as tetrabutylammonium salt, or as salts with other cations as counter ions and lithium, sodium, potassium, rubidium, cesium salt or simple ammonium salt, mono-, di- and trialkylammonium salt or hydrogen ion, hydronium ion or other hydrated proton or protonated forms, is new. Perylene bisimide radical anion (A) of formula (5), (6) or (7) as salt, preferably as tetrabutylammonium salt, or as salts with other cations as counter ions and lithium, sodium, potassium, rubidium, cesium salt or simple ammonium salt, mono-, di- and trialkylammonium salt or hydrogen ion of formula (H+>), hydronium ion of formula (H3O+>) or other hydrated proton or protonated forms, is new. R1-R8H or 37C-alkyl residue (where 1-10 CH2-units is optionally substituted by carbonyl groups, O, S, Se, Te, cis or trans-CH=CH-groups, where a CH unit is optionally substituted by N, C?=C, 1,2-, 1,3 - or 1,4-substituted phenyl residues, 2,3, 2,4, 2,5, 2,6, 3,4 - or 3,5-disubstituted pyridine residues, 2,3, 2,4, 2,5 or 3,4-disubstituted thiophene residues, 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 2,3, 2,6 or 2,7 disubstituted naphthalene residues, where one or two groups of CH is optionally substituted by N, 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 1,9, 1,10, 2,3, 2,6, 2,7, 2,9, 2,10- or 9,10- disubstituted anthracene residues, where one or two CH groups are optionally substituted by N, up to 12 H atoms of CH2-groups are optionally substituted on the same carbon atoms by halo, CN or up to 18C-alkyl, where 1-6 CH2-units are optionally substituted by carbonyl, O, S, Se, Te, cis or trans-CH=CH-groups, where a CH-unit is optionally substituted by N, C?=C, 1,2, 1,3 or 1,4-substituted phenyl residues, 2,3, 2,4, 2,5, 2,6, 3,4 - or 3,5-disubstituted pyridine residues, 2,3, 2,4, 2,5 - or 3,4-disubstituted thiophene residues, 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 2,3, 2,6 - or 2,7-disubstituted naphthalene residues, where 1-2C are optionally substituted by N, 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 1,9, 1,10, 2,3, 2,6, 2,7, 2,9, 2,10- or 9,10- disubstituted anthracene residues, where 1-2C are optionally substituted by N, up to 12 H of the CH2 of the alkyl residues are optionally substituted on the same carbon atoms by halogen, CN or up to 18C-alkyl, where 1-6 CH2-units are optionally substituted by carbonyl, O, S, Se, Te, cis or trans-CH=CH-groups, where a CH-unit is optionally substituted by N, C?=C groups of 1,2, 1,3- or 1,4-substituted phenyl residues, 2,3, 2,4, 2, 5, 2,6, 3,4- or 3,5- disubstituted pyridine residues, 2,3, 2,4, 2,5- or 3,4- disubstituted thiophene residues, 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8-2,3, 2,6 - or 2,7-disubstituted naphthalene residues, where 1-2C are optionally substituted by N, 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 1,9, 1,10, 2,3, 2,6, 2,7, 2,9, 2,10- or 9,10-disubstituted anthracene residues, where 1-2C are optionally substituted by N). Provided that the substituents are linked in pairs, in order to avoid the carrying of free valencies of methine groups and/or quaternary carbon-atoms, to form a ring, e.g. cyclohexane ring. An independent claim is included for the preparation of (A). [Image] [Image] [Image].

Description

was standing of the technique

organic Magnets have been known for several years. The representation of such But materials is relatively expensive. Easier preparative accessible Materials would be of special interest.

perylene (1), perylene-3,4: 9,10-tetracarboxylic bisimides are known for their unusual good qualities appreciated Pigments and fluorescent dyes [1] [2] [3] [4] [5] [6]. Next to her unusually high Lightfastness is also their special thermal stability to emphasize - such is their consistency up to 550 ° C been described. The durability of the dyes acids is also extremely high - so the dyes can be unscathed in conc. sulfuric acid solved and when diluting the acid get back become [8]; another proof for the durability is the technical saponification of perylene bisimide 1 (R = H), for the conc. sulfuric acid at 220 ° C needed will - others acids are ineffective [1]. They are therefore ideal materials for complex Applications. So far, however, was the application of the substances quite predominantly in the dye area [9]. Your extended electron system but should be more options open.

At first were the perylene dyes 1 shortly after their discovery as vat dyes been used. Across from However, this application has a subordinate use of them as pigments Gained importance. This is u.a. Remember that their stability against bases not so pronounced like their consistency across from acids is, so a vat dyeing, for the a strongly basic medium is preferred with these dyes is difficult. On the other hand, in previous work γ-hydroxylakyl substituents as hydrolysis stabilizing structures for perylene bisimides developed been [10] [11] [12] [13]. It is to ask to what extent a such structure on the vatting the perylene dyes.

task

The Task was to Perylenderivate with special magnetic and to develop optical properties.

description

We have treated the perylenebisimide 2a with a γ-hydroxyalkyl substituent in a strongly alkaline solution (NaOH) with hydroxyacetone analogously to Ref. [14] reducing the conversion to surprisingly smooth to a strongly colored material. This was then precipitated on the basis of Ref. [15] with tetrabutylammonium bromide. In this case, a dark blue-red material was obtained, which is indefinitely stable under inert gas and can be performed with the unexpected even simple operations in air A special packaging of the compound 3a with a corresponding counter-cation, especially their tetrabutylammonium salt, and using inert gas would Thus, it is possible to store the material in question arbitrarily and distribute and also use in portions for the various applications. Surprisingly, however, this compound (3a) is not, as would be expected in analogy to indigo, a dianion of the reduced form but the radical anion 3a; please refer 1 - in 1 only a mesomeric boundary formula is drawn; the unpaired electron or negative charge is distributed over all four carbonyl groups and over the C atoms of the aromatic system (this also applies to the following structural formulas). Typically, no signals for the anionic part are found in the ¹ H-NMR spectrum of the substance because obviously fast relaxation processes are induced there, but for the tetrabutylammonium counterion and the water of crystallization. Another indication of the structure of 3 is the anion mass spectrum, which directly provides the molecular peak. The elemental analysis of the material is additional evidence of the structure. In the IR spectrum of 3a, a considerable shift in the carbonyl frequencies of 1688 and 1638 cm ^-1 to 1601 and 1544 cm ^{-1 occurs} after low wavenumbers, whereas the C = C valence vibration remains completely unchanged. It can be assumed that the negative charge in 3a is distributed substantially over the four carbonyl groups and weakens the C = O double bond.

The most obvious evidence for the radical anions structure, however, is the comparison of the UV / Vis spectrum of the substance with the similar spectra of electrochemically generated perylenebisimide radical anions; please refer 2 , The latter could be registered spectroelectrochemically in the immediate vicinity of the cathode, first up to 800 nm [16], later up to 1000 nm [17]; see. also [18]. Because of the decomposability of such radical ions, further investigations are not possible. According to the present invention, it has therefore been possible to stabilize perylenebisimide radical anions as salts, in particular as tetrabutylammonium salts; other salts such as lithium, sodium, potassium, rubidium, cesium salts or simple ammonium salts, mono-, di- and trialkylammonium salts or even H ⁺ , H ₃ O ⁺ or other hydrated protons or protonated forms are suitable in principle. It could be shown here that the materials could easily be preserved for many months - no signs of decomposition could be detected and no end of shelf life is yet to be foreseen.

The dark crystals of 3 form deep blue solutions that are stable in the absence of oxygen, but whose color is not caused by the longest wavelength light absorption because it is shifted far into the NIR range; please refer 2 , Here is an example of the concept of 'second-order colors' developed by J. Piccard [19], where the absorption in the visible range is caused by a higher electron transition.

2 B with longer ones Leaves side chains according to the invention analog to reduce 2a to 3b, its UV / Vis spectra with those of 3a practically are congruent. The substance shows a different solution behavior as 3a. The solutions of 3 slowly oxidize under the action of atmospheric oxygen back to the starting materials; the reduction is completely reversible, since virtually no by-products are formed (DC comparison).

We have according to the present Invention also simple perylene dyes under these conditions reduced, but because of their appreciable alkalinity the sodium hydroxide exchanged for the nonionic base DBU. How to get out N, N '- (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic bisanhydride [20], which is easily soluble by the sec-alkyl groups [21], the radical anion 4, the one to 3 completely analog UV / Vis spectrum results. The substance, however, is extraordinary sensitive to oxidation. Traces of oxygen or other oxidizing agents in shielding gases or reagents, the radical 4 rapidly breaks down; this requires in practice, especially because of the high Molecular weight special protective measures for the handling of the substance. These results confirm the particular advantage of the substituents with γ-hydroxy groups.

We have treated the solid powdery material 3a with a permanent magnet, see 3a , and found that it adheres like iron filings to the magnet; the individual adhering particles follow the direction of the field lines of the magnet. For this arrangement of the particles electrostatic effects hardly come into question, because an analogous contact of 3a with non-magnetic stainless steel results only tightly fitting material, see 3b , so that obviously magnetic effects are responsible for the structuring of the powder.

magnetic, organic materials are for many areas of technology of interest. So first electronic applications in transmitters, magnetic To name filters and resonators. The low conductivity ladder Of the organic materials makes this particular for very high Frequencies interesting, because no problems by the emergence of eddy currents to be expected. Magnetic materials are also for signal recording significant. Purely organic substances can because of their problem-free Disposability in the future have special significance, for example 3a only from carbon, hydrogen oxygen and nitrogen. Furthermore is an advantage to call their low density.

experimental part

2,9-bis (2-hydroxymethyl-2-propylpentyl) anthra [2,1,9-def; 6,5,10-d'e'f '] diisoquinoline-1,3,8,10-tetraon- radical anion tetrabutylammonium salt (3a): 2,9-bis (2-hydroxymethyl-2-propylpentyl) anthra [2,1,9-def; 6,5,10-d'e'f '] diisoquinoline-1,3 , 8,10-Tetrazone 2a (60 mg, 0.09 mmol) is placed under argon and treated with 0.8 ml of degassed distilled water and 0.5 ml 30 percent. Slurried sodium hydroxide solution, heated to 40 ° C, with hydroxyacetone (0.5 mL, 7.3 mmol) added (color change to violet), stirred for 10 min, slowly added to a solution of tetrabutylammonium bromide (500 mg, 1.55 mmol) in degassed water (1 mL) (purple precipitate), with degassed distill. Water, filtered off, washed with degassed distilled water and dried in a fine vacuum. Y. 88 mg (98% based on 4.5 water of crystallization), mp> 250 ° C; IR (diamond die cell): v ~ = 3254 cm ^-1 (m, br, -OH), 2957 (s), 2871 (s), 1601 (s), 1544 (s), 1491 (w), 1435 (m, br), 1361 (m), 1327 (s), 1226 (m), 1145 (m) 1102 (w), 1057 (m), 879 (w), 788 (m), 744 (m), 701 (w ); IR (silicone oil): v ~ = 3253 (w, br, -OH), 2962 (s), 1946 (w), 1689 (w), 1603 (s), 1546 (m), 1414 (m), 1360 ( m), 1330 (w), 1261 (s), 1096 (s, br), 800 (s, br), 702 (m), 504 (w), 465 cm ^-1 (w); ¹ H-NMR (600 MHz, acetone-D ₆ , 25 ° C): δ = 0.97 (t, 12 H, J = 7.4 Hz), 7.1 Hz (N- (CH ₂ ) ₃ -C H ₃ ), 1.43 (sx, 8 H, J = 7.4 Hz, 7.1 Hz, N- (CH _{2) 2} -C H ₂ -CH _3), 1.84 (q, br, 8 H, N-CH ₂ -C H ₂ -CH ₂ -CH _3), 3:48 (t, 8 H, J = 8.2 Hz, NC H ₂ - (CH _{2) 3} -CH ₃₎ ppm; UV / Vis (acetone): λ _max (E _rel ) = 956 (0.36), 795 (0.41), 765 (0.38), 710 (0.50), 700 (0.51), 277 (0.42), 259 (0.56), 219 (0.91), 200 nm (1.00); UV / Vis (acetonitrile): λ _max (E _rel) = 957 (0.22), 797 (0:42), 766 (0:21), 711 (0.83) 703 (0.89) 277 (0:42), 260 (12:49), 220 (0.91), 200 nm (1.00); MS (FIA / ESI): m / z: 674 [M, C ₄₂ H ₄₆ O ₆ N ₂ ], 572 [C ₃₈ H ₂₄ O ₄ N ₂ ], 337 [C ₂₁ H ₂₃ O ₃ N ₁ ]; C ₅₈ H ₈₃ N ₃ O ₆ · 4.5 H ₂ O (999.3): calc. C 69.71, H 9.21, N 4.20; gef. C 69.56, H 9.44, N 4.25.

2,9-Bis (1-hexylheptyl) anthra [2,1,9-def; 6,5,10-d'e'f '] diisoquinoline-1,3,8,10-tetrazone radical anion tetrabutylammonium salt (4) : 2,9-bis (1-hexylheptyl) anthra [2,1,9-def; 6,5,10-d'e'f '] diisoquinoline-1,3,8,10-tetraone (70 mg, 0.10 mmol) is placed under Ar and slurried in 1.5 ml of ethanol and 0.2 ml DBU. It is heated to 50-55 ° C and the reducing agent hydroxyacetone (0.5 ml, 7.3 mmol) was added. Violet dyeing is observed. After stirring for 5-10 minutes, a solution of tetrabutylammonium bromide (500 mg, 1.55 mmol) in 1 ml of water is added. The mixture is then diluted with 10 ml of distilled water and the resulting suspension is cooled for 15 min with ice. The precipitate is then filtered off with suction through a P 4 Schlenk frit and dried in a fine vacuum for several hours. UV / Vis (acetonitrile): λ _max (I _rel ) = 956 (0.11), 795 (0.18), 765 (0.15), 710 (0.33), 700 (0.35), 277 (0.2), 259 (0.44), 219 nm (1.00).

Subject of the invention

• 1. perylenebisimide radical anions of the general formula 5 as salts, in particular as tetrabutylammonium salts, or as salts with other cations as counterions such as lithium, sodium, potassium, rubidium, cesium salts or simple ammonium salts, mono-, di- and trialkylammonium salts or even H ⁺ , H ₃ O ⁺ or other hydrated protons or protonated forms,
  
  in which the radicals R 1 to R 8 can be identical or different and independently of one another denote hydrogen or linear alkyl radicals having at least one and at most 37 C atoms, in which one to 10 CH ₂ units can be replaced independently by in each case carbonyl groups, oxygen atoms , Sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡C groups 1,2-, 1,3- or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5 - or 3,4-disubstituted thiophene, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2 , 6- or 2,7-disubstituted naphthalene radicals in which one or two CH groups may be replaced by nitrogen atoms, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted Anthracene residues in which one or two CH Groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups can each be independently replaced on the same carbon atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group or a li neare alkyl chain having up to 18 carbon atoms, in which one to 6 CH ₂ units may be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium, cis- or trans-CH = CH groups in which a CH May also be replaced by a nitrogen atom, acetylenic C≡C groups, 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2 , 6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1, 4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms have been replaced by nitrogen atoms may, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3 -, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which one to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit can also be replaced by a nitrogen atom, acetylenic C ≡C groups 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9-, 2,10- or r 9,10-Disubstituierte Anthracenreste in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or of the quaternary C atoms can be linked in pairs to form rings, such as cyclohexane rings. The radicals R ¹ to R ⁸ can also independently of one another denote the halogen atoms F, Cl, Br or I.
• 2. perylenebisimide radical ions of general formula 6 as salts, in particular as tetrabutylammonium salts, or as salts with other cations as counterions such as lithium, sodium, potassium, rubidium, cesium salts or simple ammonium salts, mono-, di- and trialkylammonium salts or even H ⁺ , H ₃ O ⁺ or other hydrated protons or protonated forms,
  
  in which the radicals R ¹ to R ^{7 have} the meaning given under 1.
• 3. Perylenebisimide radical ions of the general formula 7 as salts, in particular as tetrabutylammonium salts, or as salts with other cations as counterions such as lithium, sodium, potassium, rubidium, cesium salts or simple ammonium salts, mono-, di- and trialkylammonium salts or even H ⁺ , H ₃ O ⁺ or other hydrated protons or rotonated forms
  
  in which the radicals R ¹ to R ^{7 have} the meaning given under 1.
• 4. Dyes of the general formulas 5 to 7, according to claim 1-3, in those quaternary Ammonium salts are used as Gegenkationen. To be favoured quadruply alkylated ammonium salts, more preferred are ammonium salts, where four alkyl groups are present. These can be branched like iso-propyl groups its synthesis is conveniently one of the groups a benzyl group, or these can also be unbranched such as n-alkyl groups, most preferred Tetra-n-butylammonium.
• 5. Dyestuffs of the general formulas 5 to 7, according to claims 1-4, in which large-volume ions are used as cationic counterions. Examples of such counterions are cesium ions, potassium ions or quaternary phosphonium ions.
• 6. The method according to claim 1-5, characterized in that the radical ions are synthesized according to 1 to 3 by chemical reduction of the corresponding bisimides. Examples of chemical reducing agents are dithionite, metals such as iron, steel, aluminum, zinc or tin, in particular in finely divided form, or also typical compounds forming endiole or endiolate in alkaline solution, in particular low molecular weight compounds (C ₂ to C ₈ ) such as α- Hydroxyketones and α-hydroxy aldehydes such as hydroxyacetone, dihydroxyacetone, glycolaldehyde, dihydroxybutanone, 2,3-dihydroxyacrylaldehyde (triose reductone), ascorbic acid or cyclopentenediol-on (reductic acid), preferably hydroxyacetone carbohydrates and other natural compounds having unsaturated bonds.
• 7. The method according to claim 1-6, characterized that the radical ions after 1 to 3 by electrochemical reduction the corresponding bisimides are synthesized. Preferred cathode materials are lead, tin, steel, stainless steel, aluminum, copper and silver, Carbon, in particular graphite. Of course you can also use mercury and cadmium but which are characterized by a high overvoltage for environmental reasons should be avoided. It will have a temperature range of 10 to 60 ° C preferred. Preferably, the anode-electrolyte space is separated from the cathode space, so that no re-oxidation of the dye radical anions takes place. This may be by ion selective membranes, e.g. Nafion, or through diaphragms, e.g. Sound diaphragms. Especially with the the latter, the anode compartment is preferably permanently purged.
• 8. The method according to claim 1-8, characterized in that the radical ions precipitate as salts according to 1 to 3 and continue in this form are processed. Preferred precipitants are salts of the cations mentioned under 4 and 5. Here are in the precipitant preferred counterions of the cations sulfate, chloride, bromide, iodide, Nitrate, phosphate, acetate, formate and tetrafluoroborate.
• 9. The method according to claim 1-8, characterized that the radical ions according to 1 to 3 from the bisimides in question in alkaline solution be reduced. Preferred ionic alkalizing agents are sodium hydroxide, Potassium hydroxide or calcium hydroxide, most preferably sodium hydroxide. preferred nonionic alkalizers are DBU (diazabicycloundecene), DBN (diazabicyclononene) or 'proton sponge' (N, N, N ', N'-tetramethyl-1,8-diaminonaphthalene), most preferred is DBU.
• 10. Application of dyes to 1-9 as magnetic materials.
• 11. Application of dyes to 1-9 as magnetic materials in electronic components, preferably in high frequency, such as e.g. Transmitter, magnetic Filters, resonators or magnetic antennas.
• 12. Application of the dyes according to 1-9 for the production of magnets.
• 13. Application of dyes to 1-9 as materials for magnetic or electromagnetic shielding.
• 14. Application of dyes to 1-9 as magnetic materials for the Signal recording, e.g. For Magnetic tapes, Magnetic disks, hard disks and optomagnetic systems.

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LIST OF REFERENCE NUMBERS

• 1 , Synthesis of perylenebisimide radical salts 3 (the counterion is not indicated).
• 2 , UV / Vis spectrum of the perylenebisimide radical anion 3a in acetonitrile.
• 3 , a) Left: Permanent magnet with adhering material 3a. b) Right: stainless steel with adhesive material 3a.

Claims (14)

Perylenebisimide radical anions of the general formula 5 as salts, in particular as tetrabutylammonium salts, or as salts with cations other than counterions such as lithium, sodium, potassium, rubidium, cesium salts or simple ammonium salts, mono-, di- and trialkylammonium salts or even H ⁺ , H ₃ O ⁺ or other hydrated protons or protonated forms,

in which the radicals R 1 to R 8 can be identical or different and independently of one another denote hydrogen or linear alkyl radicals having at least one and at most 37 C atoms, in which one to 10 CH ₂ units can be replaced independently by in each case carbonyl groups, oxygen atoms , Sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡C groups 1,2-, 1,3- or 1, 4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5 - or 3,4-disubstituted thiophene, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2 , 6- or 2,7-disubstituted naphthalene radicals in which one or two CH groups may be replaced by nitrogen atoms, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted Anthracene residues in which one or two CH Groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group or a linear alkyl chain with up to 18 C atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9, 2, 10 or 9, 10 disubs substituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which one to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit can also be replaced by a nitrogen atom, acetylenic C ≡C groups 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9-, 2,10- or r 9,10-Disubstituierte Anthracenreste in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or of the quaternary C atoms can be linked in pairs to form rings, such as cyclohexane rings. The radicals R ¹ to In addition, R ⁸ can independently of one another denote the halogen atoms F, Cl, Br or I. Perylenebisimide radical ions of general formula 6 as salts, in particular as tetrabutylammonium salts, or as salts with cations other than counterions such as lithium, sodium, potassium, rubidium, cesium salts or simple ammonium salts, mono-, di- and trialkylammonium salts or even H ⁺ , H ₃ O ⁺ or other hydrated protons or protonated forms,

in which the radicals R ¹ to R ^{7 have} the meaning given under 1. Perylenebisimide radical ions of the general formula 7 as salts, in particular as tetrabutylammonium salts, or as salts with cations other than counterions such as lithium, sodium, potassium, rubidium, cesium salts or simple ammonium salts, mono-, di- and trialkylammonium salts or even H ⁺ , H ₃ O ⁺ or other hydrated protons or protonated forms,

in which the radicals R ¹ to R ^{7 have} the meaning given under 1. Dyes of the general formulas 5 to 7, according to Claim 1-3, in which quaternary Ammonium salts are used as Gegenkationen. To be favoured quadruply alkylated ammonium salts, more preferred are ammonium salts, where four alkyl groups are present. These can be branched like iso-propyl groups its synthesis is conveniently one of the groups a benzyl group, or these can also be unbranched such as n-alkyl groups, most preferred Tetra-n-butylammonium. Dyes of the general formulas 5 to 7, according to Claim 1-4, in which large-volume ions are used as cationic counterions. examples for such counterions are cesium ions, Potassium ions or quaternary Phosphonium. A method according to claim 1-5, characterized in that the radical ions are synthesized according to 1 to 3 by chemical reduction of the corresponding bisimides. Examples of chemical reducing agents are dithionite, metals such as iron, steel, aluminum, zinc or tin, in particular in finely divided form, or also typical compounds forming endiole or endiolate in alkaline solution, in particular low molecular weight compounds (C ₂ to C ₈ ) such as α- Hydroxyketones and α-hydroxy aldehydes such as hydroxyacetone, dihydroxyacetone, glycolaldehyde, dihydroxybutanone, 2,3-dihydroxyacrylaldehyde (triose reductone), ascorbic acid or cyclopentenediol-on (reductic acid), preferably hydroxyacetone carbohydrates and other natural compounds having unsaturated bonds. Process according to Claims 1-6, characterized in that the radical ions according to 1 to 3 are synthesized by electrochemical reduction of the corresponding bisimides. Preferred cathode materials are lead, tin, steel, stainless steel, aluminum, copper and silver, carbon, in particular graphite. Of course, mercury and cadmium can be used, which are characterized by a high overvoltage, but should be avoided for environmental reasons. A temperature range of 10 to 60 ° C is preferred. Preferably, the anode-electrolyte space is separated from the cathode space, so that no re-oxidation of the dye radical anions takes place. This can be done by ion-selective membranes, such as eg Nafion, or by diaphragms, such as clay diaphragms. Especially in the case of the latter, the anode space is preferably permanently rinsed. Method according to claims 1-8, characterized in that the radical ions precipitate as salts according to 1 to 3 and continue in this form are processed. Preferred precipitants are salts of the cations mentioned under 4 and 5. Here are in the precipitant preferred counterions of the cations sulfate, chloride, bromide, iodide, Nitrate, phosphate, acetate, formate and tetrafluoroborate. Method according to claims 1-8, characterized that the radical ions according to 1 to 3 from the bisimides in question in alkaline solution be reduced. Preferred ionic alkalizing agents are sodium hydroxide, Potassium hydroxide or calcium hydroxide, most preferably sodium hydroxide. Preferred nonionic alkalizers are DBU (diazabicycloundecene), DBN (diazabicyclononene) or 'proton sponge' (N, N, N ', N'-tetramethyl-1,8-diaminonaphthalene), most preferred is DBU. Application of the dyes according to claims 1-9 as magnetic Materials. Application of the dyes according to claims 1-9 as magnetic Materials in electronic components, preferably in high frequency, such as. Transmitter, magnetic Filters, resonators or magnetic antennas Use of the dyes according to claims 1-9 for the preparation of magnets. Use of the dyes according to claims 1-9 as materials for magnetic or electromagnetic shielding. Application of the dyes according to claims 1-9 as magnetic Materials for the signal recording, e.g. for magnetic tapes, magnetic disks, hard disks and optomagnetic systems.