DE102008036495A1 - New naphthalene, perylene, benzoperylene, terrylene, quaterrylene bisimide and trisimide anions, as salts, e.g. tetrabutylammonium- or potassium-salts, useful e.g. to prepare dyes, preferably vats dye, to color cotton, paper and nylon - Google Patents

Abstract

Naphthalene bisimide radical anions (XVI), naphthalene bisimide anions (XVII), perylene bisimide radical anions (XVIII), perylene bisimide anions (XIX), benzoperylene trisimide radical anions (XX), benzoperylene trisimide anions (XXI), terrylene bisimide radical anions (XXII), terrylene bisimide anions (XXIII), quaterrylene bisimide radical anions (XXIV), and quaterrylene bisimide anions (XXV), as salts e.g. tetrabutylammonium salt, or as salts with other cation, as counter ion e.g. lithium salt, or mono-, di- and trialkylammonium salt, are new. Naphthalene bisimide radical anions of formula (XVI), naphthalene bisimide bisanions of formula (XVII), perylene bisimide radical anions of formula (XVIII), perylene bisimide anions of formula (XIX), benzoperylene trisimide radical anions of formula (XX), benzoperylene trisimide anions of formula (XXI), terrylene bisimide radical anions of formula (XXII), terrylene bisimide anions of formula (XXIII), quaterrylene bisimide radical anions of formula (XXIV), and quaterrylene bisimide anions of formula (XXV), as salts, preferably as tetrabutylammonium salt, or as salts with other cation, as counter ion, such as lithium, sodium, potassium, rubidium, cesium salt or ammonium salt, mono-, di- and trialkylammonium salt or H +>, H 3O +>or other hydrated proton or protonated forms, are new. R 1>-R 1>4>H or linear alkyl with at least 1-37C ((in which 1-10 CH 2-units are optionally substituted by carbonyl, O, S, Se, Te, cis or trans-CH=CH-groups (in which one CH unit is optionally substituted by N)), -C?=C-, 1,2-, 1,3- or 1,4-substituted phenyl residue, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine residue, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene residue, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted napthalene residue (in which one or two CH groups 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 residue (in which one or two CH groups are optionally substituted by N), where 2-12 single hydrogen atoms of the CH 2group in the alkyl residue are optionally substituted by halo, preferably F, Cl, Br or I or CN), or linear 2-18C-alkyl (in which 1-6 CH 2units are optionally substituted by carbonyl, O, S, Se, Te, cis or trans-CH=CH-groups (in which one CH unit is optionally substituted by N), -C?=C-, 1,2-, 1,3- or 1,4-substituted phenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine, 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 (in which one or two carbon atoms 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 (in which one or two carbon atoms are optionally substituted by N), where 2-12 single hydrogen atoms of the CH 2-group of the alkyl residue are optionally substituted by halo, preferably F, Cl, Br or I, or CN), or linear 2-18C-alkyl (in which 1-6 CH 2-units are optionally substituted by carbonyl, O, S, Se, Te, cis or trans-CH=CH-groups (in which one CH unit is optionally substituted by N), -C?=C-, 1,2-, 1,3- or 1,4-substituted phenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine, 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 (in which one or two carbon atoms 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 (in which one or two carbon atoms are optionally substituted by N), where: instead carrying substituents, the free valent methine group and/or quaternary carbon atom are connected in pair-wise to form rings, e.g. cyclohexane ring, and the residue R 1>-R 6>contains halo, preferably F, Cl, Br or I). Independent claims are included for: (1) a dye comprising (XIV)-(XXV), in which quaternary ammonium salt is used as counter cation, which is four times alkylated ammonium salt, preferably strong ammonium salt with four alkyl group, optionally branched iso-propyl group, benzyl group or branched n-alkyl group, tetra-n-butyl ammonium; and (2) the preparations of (XIV)-(XXV). [Image] [Image] [Image] [Image].

Description

State of the art

long-wave Light absorptions - up into the NIR range - gain an increasing interest in basic research and also in the technique [1]. For simple organic compounds this is HOMO fully occupied and the output for the longest wave Electron transition. Unfortunately, the HOMO-LUMO distance greater than the energetic distance of the others Orbital, so that a short-wave light absorption results - more electron transitions at even shorter wavelengths. Organic substances are therefore usually colorless. Compounds that are in the visible area or even longer wavelength absorb, one builds up from extended, conjugated π-systems [2] to lower the HOMO-LUMO distance. Further bathochromic shifts be through a suitable linkage of such systems achieved with donor and acceptor groups. As innovations are here To name super-donor groups [3] and super-acceptor groups [4], with those even further, powerful bathochromic color shifts were to be reached. Because even in these cases the longest wave Light absorption is associated with the HOMO-LUMO distance It is getting more and more difficult in the even longer wave range to advance. On the other hand, in the usual organic compounds of the energetic HOMO-LUMO distance in comparison to the energetic sequence of the other orbitals largest, so that just this transition for a long-wave Absorption forms less favorable conditions. The fully occupied HOMO is inevitably the starting point for the longest wavelength electron transfer and the other orbitals, leaving other electron transitions not available with lower energy. But when the topmost occupied orbital not two electrons, but only contains one, other electron transitions become accessible with smaller energy gaps, so that a long-wavelength light absorption with considerably less effort can be reached. It is to ask, whether one is long-waved in this way can develop absorbing dyes.

task

The The object of the present invention was to absorb long-wave To develop dyes, NIR dyes, which are an unpaired electron contain.

description

For the development of NIR dyes with unpaired electrons can one basically start from known dyes and either remove an electron from the HOMO or another electron transferred to the LUMO. We chose the latter Possibility decided that a reduction of the dyes represents. In this case, however, free radicals are obtained, the very strongly prone to combination reactions. We have investigated whether to reduce such a tendency by introducing charges so that this may be the issue of the synthesis of radical anions leads.

The starting materials were the naphthalene-1,8: 4,5-tetracarboxylic bisimides 1 [5, 6], which are colorless with their longest wavelength absorption in the UVA range. A reduction of 1 to radical anion 2 is facilitated by a strongly alkaline medium; However, this is problematic for the carboxylic acid imide units of 1, since a basic cleavage can take place. In order to suppress such an interfering reaction, the nitrogen atoms in Figure 1 have been substituted with 3-hydroxypropyl groups which carry in position 2 geminal alkyl groups (1a to 1e). These groups are known to be able to protect the similar perylenetetracarboxylic bisimides from alkaline hydrolysis in such positions [7]. For this purpose, intramolecular hydrogen bonds can be made responsible for the carboxylic imide carbonyl groups. for which a sharp IR absorption at 3460 cm ^-1 and a characteristic slightly changed vibrational structure of the UV / Vis absorption are evidence. The stabilizing effect by such groups, such. B. R = 2-butyl-2-hydroxymethylhexyl (1c) is also for the Naphthalinbisimide 1 considerably, but not quite as pronounced as in the perylene dyes. To further suppress hydrolysis reactions, one can use the nonionic base DBU, which is also more lipophilic than simple alkalis such as NaOH or KOH, so that a variety of organic solvents can be used for the reaction.

We have reduced the derivative 1b with R = 2-hydroxymethyl-2-propylpentyl with the lipophilic reductone hydroxyacetone [8] using the nonionic base DBU in acetone to give a mixture of the long-wave absorbing radical anion 2b and the shorter-wavelength absorbing bisanion 3b receive. The ratio of radical anion to bisanion depends on the polarity of the solvent used. The use of acetone predominantly results in the formation of radical anion 2, in toluene approximately a 1: 1 mixture of radical 2 and bisanion 3 and in ethanol predominantly bisanion 3. The addition of the weak oxidizing agent diacetyl allows the redox potential of the mixture to be adjusted in that essentially the radical anion 2 is obtained; please refer 2 , This is visible UV / Vis spectroscopy, because the radical anion 2 absorbs surprisingly long-wave and a further reduction to 3 then again leads to a hypsochromic shift in the absorption.

The Naphthalinradikalanionen 2 can be precipitated from the alkaline solution with tetra-n-butylammonium bromide and are then obtained as surprisingly storage-stable solids, which show no decomposition in the absence of atmospheric oxygen. This is for the use of substances of particular advantage, such. B. for light absorption purposes, because they do not have to be prepared in each case via a reduction reaction. It can be demonstrated by solid UV / Vis / NIR spectroscopy that even in the solid radical anions are present, because of a similar long-wave absorption, as observed in solution; please refer 3 ,

at the benzoperylene hexycarboxylic acid trisimide 4 is the light absorption compared to 1 so long-wavy that already at the starting material the visible range is reached. It is to ask how far the absorption by a reduction to the radical anion in the long-wave Range can be moved.

Benzoperylenhexacarbonsäuretrisimide 4 are converted from perylenetetracarboxylic bisimides 7 the Clar variant of the Diels-Alder reaction with maleic acid anhydride and a subsequent condensation with primary amines shown [9]. It was tried in this way the hydrolysis stabilizing Introduce hydroxypropyl in 4. However, succeeded the reaction of maleic anhydride with such substituted perylenetetracarboxylic bisanhydride such as 7h Not; possibly the solubility is the perylenebisimides available for this reaction too small. Therefore, as an alternative by known means the easily soluble Perylenetetracarboxylic bisimide 7c with 1-hexylheptyl residues at the nitrogen atoms with maleic anhydride in known Way [9] implemented then the thus formed anhydride bisimide to condense with the branched 3-hydroxypropylamines, at least the more sensitive five-membered carboxylic acid imide To protect hydrolysis. Here was a condensation in imidazole under standard conditions [10] unsuccessful. The Implementation succeeded but using dicyclohexylcarbodiimide and trifluoroacetic acid in chloroform. The corresponding Benzoperylene hexacarboxylic acid trisimide 4a was like the naphthalene tetracarboxylic bisimides 1 reduced in acetone and leads predominantly to radical anion 5. A small addition of diacetyl shifts that Balance then completely after 5. The radical anion Like 2, 5 was precipitated with tetra-n-butylammonium bromide become. The resulting dark green solid is however considerably less resistant than 2.

The Reduction of benzoperylene hexacarboxylic acid trisimide for Radical anion 5 leads to another significant bathochromic Shift in absorption, which astonishingly already at 867 nm is located.

The Perylenetetracarbonsäurebisimide 7 absorb as a source of reductions even longer wavelength than the already presented systems 1 and 4, so that a good starting basis for long-wave absorbing materials. In the reduction of 7a, see 5 However, with hydroxyacetone using DBU, the reaction is largely to the dianion 9a, as can be seen from the UV / Vis / NIR spectrum. If the alkyl chain on the nitrogen atoms is lengthened and branched as in 7b, the proportion of radical anion 8b in equilibrium increases in proportion to bisanion 9b and increases even further at 7c. This can be attributed to the increasing electron donating effect of increasing alkyl radicals which destabilizes the dianions relative to the radical anion. The reduction of 7 by hydroxyacetone to dianion proceeds stepwise, since UV / Vis / NIR spectra of the reaction solution of 7b at 5 min intervals show that the radial anion is initially formed preferentially, but then decreases in favor of the bisanion.

Perylenebisimides are stabilized by alkyl substituents on the nitrogen atoms against alkaline hydrolysis [7], if they carry in position 3 hydroxy groups and are branched in position 2. The effect is probably due to an intramolecular hydrogen bonding of the hydroxy group to one carbonyl group, as one finds in the infrared spectrum for this a typical, sharp absorption at 3460 to 3470 cm ^-1 and in the UV / Vis spectrum compared to other N-alkyl Derivatives slightly altered vibrational structure. The stability to hydrolysis makes it possible to use for reduction either the nonionic base DBU or alkalis such as sodium hydroxide or potassium hydroxide. The hydroxy substituent in turn stabilizes the corresponding bisanions 9; please refer 6 and 7 , so that in the dyes 7d to 7f only 2 to 5% Radikalanion 8 is present in equilibrium and UV / Vis spectroscopically at 7g no radical anion was found in equilibrium. In the reduction, the redox potential of the solution can be adjusted by the addition of the weak oxidizing agent diacetyl so that in equilibrium predominantly the radical anion 8 is present; please refer 6 and 7 ,

The radical anions of perylene bisimides have been precipitated by means of tetra-n-butylammonium bromide and form dark blue solids 8, which show no decomposition in an inert atmosphere and can even be handled in the air at short notice. From atmospheric oxygen, they are slowly reoxidized to the Perylenbisimiden 7. The Radi kal character of the substances is confirmed by ESR spectroscopy. In 8th is the ESR spectrum of 8e in solution and also in solid phase.

The free electron is apparently distributed in 8 over the entire π-system, because in the radical is not only the IR carbonyl frequencies at 1600 and 1540 cm ^-1 compared to the starting material at 1688 and 1638 cm ^-1 lowered, but also the frequencies of the C = C stretching vibrations.

The light absorption of the radical anions 8 synthesized from the perylenebisimides is up to 957 nm already very long wavelength in the NIR range and has a variety of absorption bands up in the UV range; please refer 9 , The dark blue color of the Radikalianion solutions is not due to its longest wavelength absorption but to higher electron transitions. Here is the concept of second-order colors by J. Piccard [11, 12, 13, 14]. Due to the large number of absorption bands z. B. Sunlight broadband absorbed. The substances can therefore be used for efficient thermal utilization of solar energy.

It is to ask, whether with the Terrylentetracarbonsäurebisimiden 10, see 10 , which already absorb as the starting atrial at 653 nm, a longer-wave absorption can be achieved. If the dye 10a is reduced under standard conditions with hydroxyacetone and DBU in acetone, then the bisanion of the terrylene bisimide 12a is obtained, which absorbs only slightly longer wavelength than 10a at 694 nm. Here, too, the redox potential can be adjusted by adding diacetyl in such a way that the radical anion 11a is obtained, which, surprisingly, already absorbs at 1319 nm; please refer 11 ,

With the quaterrylenebisimide 13a, see 12 , a starting material is available that absorbs at 762 nm very long wavelength, and it is to ask whether the reduction can achieve a longer wavelength shift of the absorption. It is analogously reduced with DBU and hydroxyacetone to Bisanion 15a, which then absorbs at 804 nm; please refer 13 , Also in this case, the redox potential of the medium can be adjusted by adding diacetyl to obtain the radical anion 14a; please refer 14 , By precipitation with tetra-n-butylammonium bromide 14a is obtained as a solid salt, which is completely stable in storage under an inert atmosphere. The UV / VIS / NIR absorption at 1700 nm is already well within the NIR range.

For the new radical ions there are many applications in technology. So it is obvious at first, they as vat dyes use. This is of particular advantage because one for a coloring does not in every single case a vat but must directly use the reduced material can. Of particular interest is the fact that the isolated radical anions for dyeing without the use of alkali can use. This is for sensitive, alkali-labile substrates really important. Textiles treated with the radical ions could then in the usual way to the dye with atmospheric oxygen be oxidized.

The Use of the radical anions, here as well manageable solid Salts have been isolated, but is also technically interesting as such. So You can use them as free radicals for calibrating spectrometers how ESR spectrometers are used. Your slight oxidizing power can be used for the detection and determination of oxidants with high Sensitivity can be used. The radical ions of perylenebisimides are of particular interest here because, as with their oxidation the highly fluorescent perylenetetracarboxylic bisimides arise and their fluorescence with high sensitivity can be demonstrated. Will a detection in the longer-wave Spectral range necessary, then can be analogous to the radical anions the Terrylen- or Quaterrylentetracarbonsäurebisimide be resorted to.

Also, the extremely long-wave absorption of the substances is interesting for their technical application, since they absorb the sunlight in a wide spectral range and thereby harnessable; 16 , The Oxydationsempfindlichkeit the radical anions is not a fundamental obstacle, because they z. B. can be introduced into the plastic film of laminated glass so that they are protected from both sides by the silicate glass against oxygen and only the edges must be sealed airtight. This inventive incorporation of the radical anions 3, 6, 9, 12 or 15 as salts with said counterions or other counterions can, for. B. by admixing the same, preferably in a concentration to the existing plastic, in particular polyvinyl butyral composite film, which is located between the two glass panes of the laminated glass that in the spectral range to be absorbed an absorbance of 0.7 to 3.0 and preferably between 0.8 and 1.5 is reached. The mixing of the dye to plastic can be done with intimate mixing, z. B. by means of agitator or extruder, by dissolving in a solvent or by temperature-assisted melting of the plastic perform. The dye-containing layer can according to the invention z. B. by spraying, screen printing, brushing, electrophoresis and subsequent drying are applied. Analogously, according to the present invention, it is also possible to produce corresponding dye-containing layers on or between individual layers of paint on other components of automobiles and other vehicles. There are also a variety of other techniques in the art to encapsulate oxygen-sensitive things so that they can be handled uncritically. Such encapsulation techniques have been developed very widely and in many ways, in particular, also by the far advanced technology of computer hard disks.

Experimental part

2-Cyano-2-ethylbutanoic acid methyl ester [15, 16, 17, 18]: methyl cyanoacetate (18 mL, 200 mmol) and 1-bromoethane (30 mL, 400 mmol) were added under exclusion of moisture and added dropwise with gentle warming with 25 percent. Natriummethanolatlösung in methanol (91 mL, 400 mmol, 2 equiv.) Was added dropwise, refluxed for 8 h, stirred for 16 h at room temperature, to dissolve the precipitated sodium bromide with distilled water (100 mL), freed by distillation from the excess methanol and once with 100 and then extracted twice with 50 mL diethyl ether. The combined organic phases were dried with magnesium sulfate and distilled first under atmospheric pressure and then under a fine vacuum. Y. 22.1 g (143 mmol, 72%) of colorless liquid, bp 50-53 ° C (7.8-7.9 · 10 ^-2 mbar). IR (ATR): v ~ = 2977 (m), 2942 (w), 2884 (w), 2243 (w), 1741 (s), 1460 (m), 1389 (w), 1436 (w), 1352, 1332, 1315, 1236 (s), 1176 (w), 1147 (w), 1037 (w), 896 (w), 811 (w), 748 cm ^-1 (w). ¹ H-NMR (300 MHz, CDCl ₃ ): δ = 1.02 (t, 6H, ³ J = 7.4 Hz, -CH ₃ ) 1.87 (m, 4H, ³ J = 7.4 Hz, -CH ₂ ), 3.79 ppm ( s, 3H, -OCH ₃ ). ¹³ C-NMR (75 MHz, CDCl ₃ ): δ = 9.7 (-CH ₃ ), 30.4 (-CH ₂ ), 51.5 (C _qu ), 53.1 (-COOCH ₃ ), 119.0 (-CN), 169.5 ppm ( -COOCH ₃ ). MS (DEI ⁺ / 70 eV): m / z (%): 156 (5) [M ⁺ + H], 127 (6) [(M ⁺ + H) -C ₂ H ₅ ], 112 (16) 96 (100) [M ⁺ -CO ₂ CH ₃ ], 80 (6), 59 (8), 42 (10). HRMS (C ₈ H ₁₃ NO ₂ ): Ber. m / z: 155.0946, Gef. m / z: 155.0924, Δ = -1.7 mmu.

Methyl 2-cyano-2-propylpentanoate [19, 20, 21, 22, 23]: methyl cyanoacetate (18 mL, 200 mmol), 1-bromopropane (37 mL, 400 mmol) and 25 percent strength by weight. Sodium methoxide solution in methanol (91 mL, 400 mmol) were reacted and worked up analogously to methyl 2-cyano-2-ethylbutanoate.
Y. 7.8 g (60%) of colorless liquid, bp 79-81 ° C (3.0 x 10 ^-2 mbar). IR (ATR): v ~ = 2964 (m), 2936 (w), 2877 (w), 2244 (w), 1743 (s), 1466 (m), 1437 (m), 1383 (w), 1307 ( w), 1280 (w), 1226 (s), 1166 (m), 1143 (m), 1025 (w), 1006 (w), 992 (w), 940 (w), 848 (w), 792 ( w), 737 cm ^-1 (w). ¹ H-NMR (300 MHz, CDCl ₃ ): δ = 0.92 (t, 6H, ³ J = 7.5 Hz, -CH ₃ ), 1.21-1.38 (m, 2H, -CH ₂ ), 1.56 (m, 2H, -CH ₂ ), 1.72 (m, 2H, -CH ₂ ), 1.85 (m, 2H, -CH ₂ ), 3.77 ppm (s, 3H, -OCH ₃ ). ¹³ C-NMR (75 MHz, CDCl _3): δ = 13.6, 18.8, 39.5, 49.8, 53.0, 119.3, 169.7 ppm. MS (DEI ⁺ / 70 eV): m / z (%): 184 (2) [M ⁺ + H], 182 (1) [M ⁺ -H], 155 (20), 141 (26), 124 ( 59), 42 (58), 41 (100). HRMS (C ₁₀ H ₁₈ O ₂ N): Ber. m / z: 184.1293 [M ⁺ + H], Gef. m / z: 184.1362 [M ⁺ + H], Δ = 3.0 mmu.

Methyl 2-butyl-2-cyanohexanoate [17, 18, 24, 25, 26]: methyl cyanoacetate (18 mL, 200 mmol), 1-bromobutane (43 mL, 400 mmol) and 25 percent strength by weight. Sodium methoxide solution in methanol (92 mL, 400 mmol, 2 equiv.) Was reacted and worked up analogously to methyl 2-cyano-2-ethylbutanoate. Y. 34.0 g (161 mmol, 80%) of colorless liquid, bp 96-97 ° C (3.4 · 10 ^-2 mbar). IR (ATR): v ~ = 2958 (s), 2932 (s), 2864 (s), 1743 (s), 1457 (m), 1381 (w), 1213 (s), 1141 (m), 1014 ( w), 955 (w), 810 (w), 730 cm ^-1 (w). ¹ H-NMR (300 MHz, CDCl ₃ ): δ = 0.88 (t, 6H, ³ J = 7.1 Hz; -CH ₃ ), 1.15-1.38 (m, 6H, -CH ₂ ), 1.58-1.59 (m, 2H, -CH ₂ ), 1.69-1.93. (m, 4H, -CH ₂ ), 3.78 ppm (s, 3H, -OCH ₃ ). ¹³ C-NMR (75 MHz, CDCl _3): δ = 13.60 (CH _3), 22:28 (CH _2), 27.45 (CH _2), 37.21 (CH _2), 49.82 _{(C, qu.)} 53.08 (-CO ₂ CH ₃ ), 119.34 (CN), 169.79 ppm (-CO ₂ CH ₃ ). MS (DEI ⁺ / 70 eV): m / z (%) = 212 (1) [M ⁺ + H], 196 (1), 155 (39), 124 (100), 123 (97), 112 (83 ), 110 (14), 55 (18), 41 (29). HRMS (C ₁₂ H ₂₂ NO ₂ ): Ber. m / z: 212.1606 [M ⁺ + H], Gef. m / z: 212.1664 [M ⁺ + H], Δ = 1.9 mmu.

2-Cyano-2-pentylheptanoic acid methyl ester [18]: methyl cyanoacetate (18 mL, 200 mmol), 1-bromopentane (37 mL, 400 mmol, 2 equiv.) And 25 percent strength by weight. Sodium methoxide solution (91 mL, 400 mmol, 2 equiv.) Was reacted and worked up analogously to methyl 2-cyano-2-ethylbutanoate. Y. 36.1 g (151 mmol, 76%) of colorless liquid, boiling point 109 ° C. (9 × 10 ^-3 mbar). IR (ATR): v ~ = 2956 (m), 2930 (m), 2862 (m), 2244 (w), 1744 (s), 1458 (w), 1237 (m), 1158 (w), 1141 cm ^-1 (w). ¹ H-NMR (600 MHz, CDCl ₃ ): δ = 0.88 (t, 6H, ³ J = 7.4 Hz, -CH ₃ ) 1.30 (m, 10H, -CH ₂ ), 1.55 (m, 2H, -CH ₂ ), 1.76 (m, 4H, -CH ₂ ), 1.88 (dt, 4H, ³ J = 4.0 Hz, ² J = 13.3 Hz -CH ₂ ) 3.81 ppm (s, 3H, -OCH ₃ ). ¹³ C-NMR (150 MHz, CDCl _3): δ = 13.8, 22.3, 25.1, 31.3, 37.5, 50.0, 53.17, 119.5, 169.9 ppm. MS (DEI ⁺ / 70 eV): m / z (%) = 240 (12) [M ⁺ ], 169 (33) [M ⁺ -C ₅ H ₁₁ ], 141 (54), 138 (63) [M ⁺ -C ₆ H ₁₃ O], 137 (100), 112 (57), 110 (27) [M ⁺ -CO ₂ CH ₃ , -C ₅ H ₁₁ ], 41 (21) [C ₂ H ₃ N ⁺ ]. HRMS (C ₁₄ H ₂₅ NO ₂ ): Ber. m / z: 239.1885, Gef. m / z: 239.1859, Δ = -2.1 mmu.

Methyl 2-cyano-2-octyldecanoate: methyl cyanoacetate (18 mL, 200 mmol), 1-bromooctane (70 mL, 400 mmol) and 25 percent strength by weight. Sodium methoxide solution in methanol (91 mL, 400 mmol, 2 equiv.) Was reacted and worked up analogously to methyl 2-cyano-2-ethylbutanoate. Y. 43.53 g (135 mmol, 67%) of colorless liquid, bp 155-162 ° C (9 x 10 ^-3 -1.6 x 10 ^-2 mbar). IR (ATR): v ~ = 2955 (s), 2925 (s), 2856 (s), 2244 (w), 1745 (s), 1458 (m), 1379 (w), 1232 (m), 1177 (w), 1137 (w), 1079 (w), 775 (w), 723 cm ^-1 (w). ¹ H-NMR (600 MHz, CDCl ₃ ): δ = 0.88 (t, 6H, ³ J = 7.0 Hz, -CH ₃ ) 1.30 (m, 10H, -CH ₂ ), 1.55 (m, 2H, -CH ₂ ), 1.76 (m, 4H, -CH ₂ ), 1.88 (dt, 4H, ³ J = 4.0 Hz, ² J = 13.3 Hz -CH ₂ ) 3.81 ppm (s, 3H, -OCH ₃ ). ¹³ C-NMR (150 MHz, CDCl _3): δ = 14.1, 22.6, 25.4, 29.1, 29.2, 31.8, 50.0, 53.2, 119.5, 169.9 ppm. MS (DEI ⁺ / 70 eV): m / z (%) = 324 (1), 323 (3) [M ⁺ ], 322 (3), 264 (15) [M ⁺ -CO ₂ CH ₃ ], 212 (7), 211 (42) [M ⁺ -C ₈ H ₁₇ ], 210 (6), 156 (9), 155 (100) [M ⁺ -C ₈ H ₁₇ , -CO ₂ CH ₃ ], 154 ( 14), 39 (18). HRMS (C ₂₀ H ₃₇ NO ₂ ): Ber. m / z: 323.2824, Gef. m / z: 323.2836, Δ = 1.2 mmu. C ₂₀ H ₃₇ NO ₂ (323.5): Ber. C 74.25, H 11.53, N 4.33; Gef. C 74.29, H 11.41, N 4.30.

2-Aminomethyl-2-ethylbutan-1-ol [27, 28, 29]: Lithium aluminum hydride (LiAlH ₄ , 7.00 g, 210 mmol, 1.5 equiv.) Was suspended under argon protective atmosphere in dry tert-butyl methyl ether (100 mL), with further tert-butyl methyl ether (50 mL), treated dropwise with 2-cyano-2-ethylbutanoate (21.0 g, 140 mmol.) And then with more Lithiumaluminiumhydrd (0.40 g, 11 mmol), heated for one hour to boiling, 16 h at Stirred room temperature, carefully under vigorous stirring and ice cooling with distilled water (6 mL), 2N NaOH (6 mL) and again with distilled water (20 mL). The precipitate was filtered off, boiled three times with tert-butyl methyl ether (50 mL each time) and discarded. The combined organic phases were washed with distilled water, dried (MgSO ₄ ) and then distilled at normal pressure and finally in a fine vacuum. Y. 6.32 g (48.0 mmol, 34%) of colorless liquid, bp 70-78 ° C (3.9 x 10 ^-2 mbar). IR (ATR): v ~ = 3369 (s, br), 3299 (s, br), 2962 (s), 2918 (s), 2878 (s), 2863 (s), 1599 (w), 1460 (m ), 1380 (m), 1166 (vw), 1060 (m), 1028 (m), 984 (w), 914 (m), 786 (w), 718 cm ^-1 (w). ¹ H-NMR (300 MHz, CDCl ₃ ): δ = 0.71 (t, 6H, ³ J = 7.5 Hz, -CH ₃ ), 1.12-1.28 (m, 4H, -CH ₂ ), 2.41 (s, 2H, -CH ₂ -NH ₂ ), 3.56 ppm (s, 2H, -CH ₂ -OH). ¹³ C-NMR (75 MHz, CDCl _3): δ = 7.1, 23.3, 39.3, 48.5, 69.4 ppm. MS (DEI ⁺ / 70 eV): m / z (%): 172 (1), 157 (9), 156 (83), 142 (8), 126 (34), 114 (23), 97 (7) , 84 (24), 71 (100), 58 (91), 55 (51).

2-aminomethyl-2-propylpentan-1-ol [18, 30]: methyl 2-cyano-2-propylpentanoate (17.8 g, 97.0 mmol) and LiAlH ₄ (5.90 g, 155 mmol) were prepared according to 2-aminomethyl-2-ol reacted ethylbutan-1-ol and worked up. Y. 16.0 g (88 mmol, 91%) of colorless liquid, b.p. 82-86 ° C (6 × 10 ^-3 mbar). IR (ATR): v ~ = 3372 (br, m), 3295 (br, m), 2955 (s), 2929 (s), 2870 (s), 1599 (w), 1465 (m), 1456 (m ), 1377 (w), 1161 (w), 1046 (m), 934 (w), 897 (w), 837 (w), 739 cm ^-1 (w). ¹ H-NMR (CDCl ₃ ): δ = 0.83 (m, 6H, -CH ₃ ), 1.16 (m, 8H, -CH ₂ ), 2.68 (s, 2H, -CH ₂ -NH ₂ ), 3.47 ppm ( s, 2H, -CH ₂ -OH).

2-Aminomethyl-2-butylhexan-1-ol [18, 30]: 2-butyl-2-cyanohexanoic acid methyl ester (20.9 g, 99.0 mmol, 1 equiv) and LiAlH ₄ (4.33 g, 115 mmol, 1.1 equiv.) reacted according to 2-aminomethyl-2-ethylbutan-1-ol and worked up. Y. 13.9 g (82.7 mmol, 55%) of colorless liquid. Bp 135-145 ° C (3.6 x 10 ^-1 mbar). IR (ATR): v ~ = 2955 (s), 2926 (s), 2859 (s), 1466 (m), 1378 (w), 1050 cm ^-1 (m). ¹ H-NMR (300 MHz, CDCl ₃ ): δ = 0.87 (t, 6H, ³ J = 7.0 Hz, -CH ₃ ), 1.03-1.30 (m, 8H, -CH ₂ ), 2.72 (s, 2H, -CH ₂ -NH ₂ ), 3.51 ppm (s, 2H, -CH ₂ -OH).

2-Aminomethyl-2-pentylheptan-1-ol [18]: 2-Cyano-2-pentylheptanoic acid methyl ester (36.2 g, 151 mmol) and LiAlH ₄ (7.45 g, 196 mmol) were correspondingly 2-aminomethyl-2-ethylbutaan-1 -ol implemented and worked up. Y. 17.8 g (82.7 mmol, 55%) of colorless liquid; Bp 164-180 ° C (6.2 x 10 ^-2 mbar). IR (ATR): v ~ = 3369 (br, m), 3299 (br, m), 2955 (s), 2926 (s), 2858 (s), 1466 (m), 1378 (w), 1056, 903 (w), 831 (w), 725 cm ^-1 (w). ¹ H-NMR (300 MHz, CDCl ₃ ): δ = 0.91 (t, 6H, ³ J = 6.9 Hz, -CH ₃ ), 1.28 (m, 16H, -CH ₂ ), 2.77 (s, 2H, -CH ₂ -NH ₂ ), 3.55 ppm (s, 2H, -CH ₂ -OH). ¹³ C-NMR (75 MHz, CDCl _3): δ = 14.0, 22.5, 22.6, 31.8, 32.7, 49.9, 71.0 ppm. MS (DEI ⁺ / 70 eV): m / z (%): 224 (19) [M ⁺ + CH ₂ O], 210 (8), 184 (18), 168 (34), 154 (18), 140 (4), 128 (3), 112 (9), 97 (17), 84 (15), 71 (72), 56 (31).

2-Aminomethyl-2-octyldecano-1-ol: 2-cyano-2-octyldecanoic acid methyl ester (38.8 g, 120 mmol, 1 equiv.) And LiAlH ₄ (5.92 g, 156 mmol, 1.3 equiv.) Were prepared according to 2-aminomethyl- 2-ethylbutan-1-ol reacted and worked up and further purified by Kugelrohr distillation in a fine vacuum. Y. 24.5 g (81.7 mmol, 68%) of colorless liquid, bp 205-225 ° C (1 x 10 ^-3 -2 x 10 ^-3 mbar). IR (ATR): v ~ = 3368 (w, br), 3300 (w, br), 1596 (w), 1466 (m), 1378 (w), 1051 (m), 721 cm ^-1 (w). ¹ H-NMR (600 MHz, CDCl ₃₎ δ = 0.88 (t, 6H, ³ J = 7.0 Hz, _-CH3), 1.26 (m, 28H, CH _2), 2.77 (s, 2H, -CH ₂ -NH ₂ ), 3.56 ppm (s, 2H, -CH ₂ -OH). ¹³ C-NMR (150 MHz, CDCl _3): δ = 14.1, 22.7, 23.0, 29.3, 29.6, 30.6, 31.9, 50.1, 71.5 ppm. C ₂₀ H ₄₅ NO (315.6): Ber. C 76.12, H 14.37, N 4.44; Gef. C 76.42, H 13.93, N 4.51.

2,7-Bis (2-ethyl-2-hydroxymethylbutyl) benzo [lmn] [3,8] phenanthroline-1,3,6,8-tetraone (1a): isochromene [6,5,4-def] isochromoenes -1,6,8-tetrazone (410 mg, 1.53 mmol), 2-aminomethyl-2-ethylbutan-1-ol (600 mg, 4.60 mmol) and DMF (25 mL) were placed under a nitrogen blanket and 2 h Boiled under reflux at 110 ° C (color change to red), allowed to cool, cautiously with 2N HCl (50 mL) with ice cooling, filtered off with suction, with little distill. Water, dried in a drying oven (80 ° C), dispersed in a little methanol, 1 h with 10% K ₂ CO ₃ , filtered off, washed with methanol / water 1: 1, dried in a drying oven at 80 ° C. Y. 202 mg (26%) of a light pink solid, mp 255-258 ° C. IR (ATR): v ~ = 3550 (s), 3508 (m), 2967 (s), 2883 (m), 1702 (s), 1657 (s), 1580 (m), 1549 (w), 1454 (m), 1428 (w), 1372 (m), 1329 (s), 1247 (m), 1168 (w), 1105 (w), 1030 (w), 1001 (w), 889 (w), 772 cm ^-1 (m). ¹ H-NMR (CDCl ₃ , 600 MHz): δ = 0.94 (t, 12H, ³ J = 7.5 Hz, -CH ₃ ), 1.32 (qd, 1H, ³ J = 7.5 Hz, ² J = 14.7 Hz, CH ₂ -), 1:41 (qd, 4H, ³ J = 7.5 Hz, ² J = 14.9 Hz, -CH ₂ -), 3.23 (d, 4H, ³ J = 7.6 Hz, -CH ₂ -OH), 3.62 ( t, 2H, ³ J = 7.6 Hz, -CH ₂ -OH), 8.79 (s, 4H, CH _ar) ppm. ¹³ C-NMR (CDCl _3, 600 MHz): δ = 7.4, 23.7, 43.1, 43.7, 65.2, 126.5, 126.6, 131.6, 164.3 ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 383, 362, 344 MS nm (ESI): m / z (%) = 641 (82) [M ⁺ + ³⁵ Cl ^-], 605 (47th ) [M ⁺ -H ⁺ ].

2,7-Bis (2-hydroxymethyl-2-propylpentyl) benzo [lmn] [3,8] phenanthroline-1,3,6,8-tetraone (1b): isochromeno [6,5,4-def] isochromene -1,3,6,8-tetrazone (655 mg, 2.45 mmol); 2-Aminomethyl-2-propylpentan-1-ol (1.17 g, 7.34 mmol) and DMF (75 mL) were prepared analogously to 2,7-bis (2-ethyl-2-hydroxymethylbutyl) benzo [lmn] [3,8 ] phenantroline-1,3,6,8-tetraone and worked up. Y. 750 mg (56%) of light pink shiny solid, mp. 199-201 ° C. IR (ATR): v ~ = 3478 (s), 2953 (s), 2928 (m), 2871 (m), 1698 (s), 1642 (s), 1582 (m), 1458 (m), 1433 ( m), 1374 (m), 1330 (s), 1244 (m), 1202 (m), 1161 (w), 1094 (m), 1039 (w), 1016 (m), 975 (w), 890 ( w), 860 (w), 776 (m), 720 (w), 662 cm ^-1 (w). ¹ H-NMR (300 MHz, CDCl ₃ ): δ = 0.94 (t, 12H, ³ J = 7.3 Hz, -CH ₃ ,), 1.34 (m, 16H, -CH ₂ ), 1.50 (m, 4H, - CH ₂ ), 3.20 (d, 4H, ³ J = 7.6 Hz -CH ₂ -OH,), 3.70 (t, 2H, ³ J = 7.6 Hz, -CH ₂ -OH,), 4.20 (s, 4H, - CH ₂ -NR ₂ ), 8.79 ppm (s, 4H, CH _ar ). ¹³ C-NMR (600 MHz, CDCl _3): δ = 14.96, 16:28, 34.38, 43.25, 43.99, 65.68, 126.5, 131.6, 164.3 ppm. UV / Vis (CHCl ₃ ): λ _max (ε) = 383 (26,600), 362 (22,000), 344 nm (13400 L · mol ^-1 · cm ^-1 ). MS (DEI ⁺ , 70 eV): m / z (%) = 550 (15) [M ⁺ ], 520 (100) [M ⁺ -CH ₃ O], 422 (7), 410 (12), 409 ( 53), 294 (9), 281 (13), 268 (6). C ₃₂ H ₄₂ N ₂ O ₆ (550.7) Ber. C 69.79, H 7.69, N 5.09; Gen. C 69.42, H 7.69, N 4.96

2,7-Bis (2-butyl-2-hydroxymethylhexyl) benzo [lmn] [3,8] phenanthroline-1,3,6,8-tetraone (1c): isochromeno [6,5,4-def] isochromene -1,3,6,8-tetrazone (1.31 g, 4.89 mmol), 2-aminomethyl-2-butylhexan-1-ol (2.75 g, 14.7 mmol, 3 equiv.) And DMF (70 mL) were analogously to 2 , 7-bis (2-ethyl-2-hydroxymethylbutyl) benzo [lmn] [3,8] phenanthroline-1,3,6,8-tetraone reacted and worked up. Y. 985 mg (1.62 mmol, 33%) of a colorless shiny solid, mp 232-234 ° C. IR (ATR): v ~ = 3480 (s), 2953 (s), 2930 (s), 2864 (m), 1698 (s), 1646 (s), 1581 (m), 1459 (m), 1432 ( m), 1367 (m), 1330 (s), 1244 (s), 1199 (w), 1150 (w), 1099 (w), 1024 (m), 884 (w), 865 (w), 776 ( w), 720 (w), 660 cm ^-1 (w). ¹ H-NMR (CDCl _3, 600 MHz): δ = 0.92 (t, 12H, ³ J = 7.1 Hz, -CH _3), 1:22 to 1:33 (m, 20H, -CH ₂ -), 1:38 to 1:46 (m , 4H, -CH ₂ -), 3.21 (d, 4H, ³ J = 7.6 Hz, -CH ₂ -OH), 3.67 (t, 2H, ³ J = 7.6 Hz, -CH ₂ -OH), 4.21 (s , 4H, -CH ₂ -NR ₂ ), 8.79 ppm (s, 4H, CH _ar ). ¹³ C-NMR (CDCl _3, 600 MHz): δ = 14.7, 23.60, 25.1, 31.65, 43.02, 43.98, 65.70, 126.51, 131.58, 164.25 ppm. MS (ESI): m / z (%): 641 (82) [M ⁺ + ³⁵ Cl ^- ], 605 (47) [M ⁺ - H ⁺ ]. UV / Vis (CHCl ₃ ): λ _max (ε) = 383 (26,600), 362 (21,900), 344 nm (13400 L · mol ^-1 · cm ^-1 ). C ₄₀ H ₄₂ N ₂ O ₆ (606.8): Ber. C 71.60, H 4.62, N 8.31; Gef. C 71.11, H 4.62, N 8.37.

Bis- (2-butyl-2-hydroxymethylhexyl) benzo [lmn] [3,8] phenanthroline-1,3,6,8-tetraone (1d): isochromeno [6,5,4-def] isochromene-1,3 , 6,8-tetrazone 13 (1.31 g, 4.89 mmol), 2-aminomethyl-2-pentylheptan-1-ol (3.16 g, 14.7 mmol, 3 equiv.) And DMF (75 mL) were prepared analogously to 2.7- Reacted bis (2-ethyl-2-hydroxymethylbutyl) benzo [lmn] [3,8] phenanthroline-1,3,6,8-tetraone and worked up. Y. 575 mg (867 μmol, 18%) of a colorless shiny solid, mp 226-229 ° C. IR (ATR): v ~ = 3486 (s), 2930 (s), 2862 (m), 1698 (s), 1644 (s), 1581 (m), 1460 (m), 1431 (w), 1413 ( w), 1369 (w), 1330 (s), 1242 (m), 1209 (w), 1191 (w), 1150 (w), 1104 (w), 1058 (w), 1026 (m), 890 ( w) 863 (vw), 778 (w) 719 (w) 662 cm ^-1 (w). ¹ H-NMR (CDCl _3, 600 MHz): δ = 0.92 (t, 12H, ³ J = 7.2 Hz, -CH _3), 1:19 to 1:37 (m, 28H, -CH ₂ -), 1:38 to 1:48 (m , 4H, -CH ₂ -), 3.20 (d, 4H, ³ J = 7.6 Hz, -CH ₂ -OH), 3.65 (t, 2H, ³ J = 7.6 Hz, -CH ₂ -OH), 8.79 ppm ( s, 4H, CH _ar ). ¹³ C-NMR (CDCl _3, 600 MHz): δ = 12.14, 22:59, 31.95, 32.79, 43.10, 65.72, 126.50, 131.57, 164.24 ppm. UV / Vis (CHCl ₃ ): λ _max (ε) = 383 (26,600), 362 (22,000), 344 nm (13800 L · mol · cm ^-1 ). MS (ESI): m / z (%): 641 (82) [M ⁺ + ³⁵ Cl ^- ], 605 (47) [M ⁺ -H ⁺ ]. C ₄₀ H ₅₈ N ₂ O ₆ (662.9): Ber. C 72.47, H 8.82, N 4.23: Gef. C 72.41, H 8.72, N 4.16.

2,7-Bis- (2-hydroxymethyl-2-octyldecyl) benzo [lmn] [3,8] phenanthroline-1,3,6,8-tetraone (1e): Under nitrogen, isochromeno [6,5,4- def] isochromene-1,3,6,8-tetrazone 13 (1.50 g, 5.59 mmol) and 2-aminomethyl-2-octyldecan-1-ol 4e (5.30 g, 16.8 mmol, 3 equiv.) and DMF (170 mL reacted analogously to 2,7-bis (2-ethyl-2-hydroxymethylbutyl) benzo [lmn] [3,8] phenanthroline-1,3,6,8-tetrazone and worked up twice, recrystallized twice from chloroform (silica gel 60, CHCl ₃ / H ₃ CCO ₂ H 50: 1), yielding 1.74 g (2.09 mmol, 37%) of a light pink shiny solid, mp 176-178 ° C. R _f value (silica gel, CHCl ₃ / H ₃ CCO ₂ H 50: 1): 0.5 IR (ATR): v ~ = 3481 (s), 2956 (m), 2921 (s), 2852 (s), 1699 (s), 1645 (s), 1580 ( s), 1460 (s), 1432 (w), 1415 (w), 1387 (w), 1370 (w), 1331 (s), 1255 (w), 1245 (m), 1191 (w), 1152 ( w), 1112 (w), 1094 (w), 1027 (w), 975 (w), 891 (w), 865 (w), 815 (w), 779 (w), 720 cm ^-1 (w) . ¹ H-NMR (600 MHz, CDCl _3): δ = 0.88 (t, 12H, ³ J = 7.0 Hz, -CH _3), 1:20 to 1:33 (m, 50H, -CH ₂ -), 1.36-1.45 (m, 4H, -CH ₂ -), 1.54-1.60 (m, 2H, -CH ₂ -), 3.20 (s, 4H, -CH ₂ -NR ₂ ), 3.66 (s, br, 2H, -OH), 8.79 ppm (s, 4H, CH _ar ). ¹³ C-NMR (600 MHz, CDCl _3): δ = 11.14, 22.66, 22.89, 29.31, 29.51, 29.53, 30.55, 30.57, 31.87, 31.95, 31.98, 43.08, 43.97, 65.69, 126.48, 131.56, 164.21, 164.23 ppm , UV / Vis (CHCl ₃ ): λ _max (ε) = 383 (26,900), 362 (22,300), 344 nm (14,000 L · mol ^-1 · cm ^-1 ). MS (ESI): m / z (%): 865.6 (100) [M ⁺ + ³⁵ Cl ^- ], 830.6 (44) [M ⁺ -H ⁺ ]. HRMS (C ₅₂ H ₈₁ N ₂ O ₅ ): Ber. m / z: 831.6173, Gef .: m / z: 831.6290, Δ = 1.1 mmu. C ₅₂ H ₈₂ N ₂ O ₆ (831.2): Ber. C 75.14, H 9.94, N 3.37; Gef. C 75.15, H 10.18, N 3.36.

N, N'-bis (1-hexylheptyl) benzo [g, h, i] perylene-2,3,8,9,11,12-hexacarboxylic acid-2,3; 8,9-bis (dicarboximide) -11, 12-anhydride: 2,9-bis (1-hexylheptyl) anthra [2,1,9-def, 6,5,10-d'e'f '] diisoquinoline-1,3,8,10-tetrazone ( 4.00 g, 5.30 mmol) was initially charged with maleic anhydride (26.0 g, 265 mmol) and heated, at an internal temperature of 110 ° C, with chloranil (2.58 g, 10.6 mmol), four days at 170 ° C bath temperature (125 ° C Internal temperature), the still warm mixture was dispersed in acetone, poured into 2N hydrochloric acid (330 mL), stirred for three days, filtered off, dried, chromatographed (silica gel, chloroform to separate the starting materials and chloroform / glacial acetic acid 10: 1 to collect the product ), taken up in a little chlorine form, precipitated with plenty of methanol, filtered off with suction and dried in a drying oven. Y. 3.56 g (79%) of yellow solid. R _f (silica gel, CHCl ₃ / H ₃ CCOOH): 0.8. IR (ATR): v ~ = 2954 (s), 2924 (s), 2855 (s), 1844 (m), 1768 (s), 1705 (s), 1658 (s), 1624 (m), 1595 ( m), 1523 (w), 1458 (m), 1414 (m), 1365 (m), 1319 (s), 1296 (m), 1281 (m), 1248 (w), 1201 (m), 1164 ( m), 1124 (w), 909 (m), 860 (w), 813 (m), 764 (m), 749 (w), 724 (w), 692 cm ^-1 (w). ¹ H-NMR (600 MHz, CDCl ₃ ): δ = 0.82 (t, 12H, ³ J = 7.0 Hz, -CH ₃ ), 1.14-1.47 (m, 32H, -CH ₂ ), 1.96 (m, 4H, NR ₂ -CH-CH ₂ ), 2.34 (m, br, 4H, NR ₂ -CH-CH ₂ ), 5.31 (m, br, 2H, R ₂ N-CH), 9.28 (s, 2H, -CH _ar ), 9.51 (d, 2H, ³ J = 8.4 Hz, -CH _ar ), 10.33 ppm (s, 2H, CH _ar ). ¹³ C-NMR (150 MHz, CDCl _3): δ = 02.14, 21.78, 26.98, 29.20, 31.75, 32.41, 55.48, 123.44, 124.69, 125.07, 127.41, 128.07, 129.20, 133.62, 162.32 ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 332 (0.46), 370 (0.03), 413 (0:28), 438 (0.68), 468 nm (1.00). Fluorescence (CHCl ₃ ): λ _max = 477 nm, 511. MS (ESI): m / z: 887.4, 886.4, 885.4, 883.4 [M ⁺ + ³⁵ Cl ^- ], 851.5, 850.4 [M ⁺ ], 849.4 [M ⁺ -H].

N, N '' - bis (1-hexylheptyl) -N '(2-hydroxymethyl-2-octyldecyl) benzoperylene-1', 2 ': 3,4: 9,10-hexacarboxylic acid-1', 2 ': 3,4: 9,10-tris- (dicarboximide) (4a): N, N'-bis (1-hexylheptyl) benzo [g, h, i] perylene-2,3,8,9,11,12- 2,3-bis (dicarboximide) -11,12-anhydride (500 mg, 590 μmol), dicyclohexylcarbodiimide (609 mg, 295 μmol) and 2-aminomethyl-2-octyldecan-1-ol (931 mg, 295 μmol) were dissolved in chloroform (18 ml), admixed with three drops of trifluoroacetic acid, refluxed for 18 hours, allowed to cool, treated with distilled water (80 ml), stirred at room temperature for three hours, with chloroform (350 ml) extracted, extracted three times with 2 N hydrochloric acid (300 mL), dried over magnesium sulfate, evaporated in vacuo, taken up in a little chloroform, precipitated by addition of much methanol, filtered off with suction, chromatographed twice (silica gel, chloroform to remove the starting material and silica gel, isohexane for removing aliphatic by-products and Eluti on the main product with toluene), taken up in a little chloroform, precipitated with methanol, filtered off with suction and dried in a dryscharank. Y. 137 mg (21%) of yellow solid, mp 289-292 ° C. R _f (toluene): 0.5. IR (ATR): v ~ = 3551 (m), 2955 (s), 2924 (s), 2855 (s), 1766 (w), 1707 (m), 1663 (m), 1625 (w), 1596 ( w), 1523 (w), 1457 (w), 1414 (w), 1397 (w), 1364 (w), 1316 (m), 1239 (w), 1175 (w), 1103 (w), 945 ( w), 845 (w), 812 (w), 764 (w), 747 cm ^-1 (w). ¹ H-NMR (600 MHz, CDCl ₃ ): δ = 0.84 (t, 12H, ³ J = 7.0 Hz, -CH ₃ ), 0.89 (t, 6H, ³ J = 6.9 Hz, -CH ₃ ), 1.23- 1.58 (m, 56H, -CH ₂ ), 2.01 (m, br, 4H, NR ₂ -CH-CH ₂ ), 2.38 (m, br, 4H, NR ₂ -CH-CH ₂ ), 3.39 (s, 2H , -CH ₂ -OH), 3.73 (s, br, 1H, -CH ₂ -OH), 3.93 (s, 2H, -CH ₂ -NR ₂ ), 9.10 (s, br, 2H, CH _ar ), 9.18 (s, br, 2H, CH _ar ), 10.22ppm (s, br, 2H, CH _ar ). ¹³ C-NMR (150 MHz, CDCl _3): δ = 14.0, 22.7, 27.1, 29.3, 29.4, 29.7, 30.6, 31.8, 31.9, 42.9, 55.4, 65.5, 122.9, 123.8, 124.4, 127.0, 127.4, 132.8, 169.6 ppm. UV / Vis (CHCl ₃ ): λ _max (ε) = 379 nm (43,000), 411 (16,000), 436 (39,000), 466 (61,000 L · mol ^-1 · cm ^-1 ). Fluorescence (CHCl ₃ ): λ _max = 475, 509 nm. Fluorescence quantum eff. (CHCl ₃ , E = 0.0338 cm ^-1 , λ _exc = 435 nm, reference perylene-3,4: 9,10-tetracarboxylic _{acid tetramethyl ester} with Φ = 100%) 32%. MS (DEI ⁺ , 70 eV): m / z (%): 1132.1 (29), 1131.1 (29), 1130.1 (64), 1129.1 (83) [M ⁺ ], 1116.1, 1099.1 (46), 950.1 (13 ), 949.1 (37), 948.1 (61), 917.1 (46), 861.1 (27), 860.1 (21), 737.1 (46), 735.1 (38), 680.0 (49), 679.0 (81), 678.0 (42 ), 666.0 (25), 509.9 (11), 499.0 (19), 498.0 (58), 496.9 (100), 495.9 (74), 483.9 (58), 482.9 (34), 414.0 (18), 111.2 (17 ), 83.2 (35), 69.2 (47). HRMS / ESI (C ₇₃ H ₁₀₁ N ₃ O ₇ ): Ber. m / z: 1131.7640, Gef. m / z: 1131.7643, Δ = 0.3 mmu. C ₇₃ H ₁₀₁ N ₃ O ₇ (1130.5): Ber. C 77.41, H 8.99, N 3.71; Gen. C 76.82, H 8.93, N 3.65.

2,9-bis (2-ethyl-2-hydroxymethylbutyl) anthra [2,1,9-def; 6,5,10-d'e'f '] diisoquinoline-1,3,8,10-tetrazone ( 7d) [18]: perylene-3,4,9,10-tetracarboxylic acid 3,4: 9,10-bisanhydride (860 mg, 2.2 mmol), 2-aminomethyl-2-ethylbutan-1-ol (6.6 mmol, 2 equiv.) And imidazole (15 g) were placed under nitrogen protective atmosphere and heated for 1 h at 140 ° C, warm while 2N HCl (200 mL), filtered off, dried at 80 ° C in a drying oven, in a few mL Methanol dispersed, 2 h with 10 percent. K ₂ CO ₃ boiled, filtered off, washed with distilled water and dried again at 80 ° C in a drying oven. Y. 1.00 g (1.62 mmol, 74%) of a red solid, mp> 400 ° C. IR (ATR): v ~ = 3466 (s), 2961 (m), 2938 (w), 2864 (m), 1698 (s), 1643 (s), 1592 (s), 1576 (s), 1507 ( w), 1443 (m), 1421 (m), 1403 (s), 1370 (s), 1335 (s), 1296 (w), 1243 (s), 1208 (w), 1170 (w), 1152 ( w), 1124 (w), 1114 (w), 1071 (m), 1049 (m), 1004 (m), 972 (s), 938 (m), 910 (w), 871 (w), 863 ( w), 849 (m), 809 (s), 795 (m), 752 (s), 713 cm ^-1 (m). ¹ H-NMR (400 MHz, D ₂ SO ₄ ): δ = 1.65 (t, 12H, ³ J = 7.3 Hz, -CH ₃ ), 2.16-2.37 (m, br, 8H, -CH ₂ ), 4.08 (s, 4H, -CH ₂ -OH), 5.52 (s, 4H, -CH ₂ -NR ₂ ), 9.63-9.80 ppm (m, 8H, CH _ar ). UV / Vis (H ₂ SO _4): λ _max (E _rel) = 601 (1.00), 556 (12:55), 521 nm (sh, 0:19.). Fluorescence (H ₂ SO ₄ ): λ _max = 616, 644 nm. MS (DEI ⁺ / 70 eV) m / z (%): 619 (35), 618 (80) [M ⁺ ], 588 (59) [ M ⁺ -CH ₂ OH], 517 (13), 505 (23) [M ⁺ -C ₇ H ₁₄ OH], 488 (17), 419 (17), 418 (53), 404 (100), 390 ( 54) [M ⁺ -2 C ₇ H ₁₄ OH], 373 (22), 345 (23), 55 (22). HRMS (C ₃₈ H ₃₈ N ₂ O ₆ ): Ber. m / z: 618.2730, Gef. m / z: 618.2719, Δ = -1.1 mmu

2,9-bis (2-hydroxymethyl-2-propylpentyl) anthra [2,1,9-def; 6,5,10-d'e'f '] diisoquinoline-1,3,8,10-tetrazone ( 7c) [18]: perylene-3,4,9,10-tetracarboxylic acid 3,4: 9,10-bisanhydride (2.0 g, 5.1 mmol), 2-aminomethyl-2-propylpentan-1-ol (1.91 g, 12.0 mmol) and imidazole (25 g) were prepared analogously to 2,9-bis (2-ethyl-2-hydroxymethylbutyl) anthra [2,1,9-def; 6,5,10-d'e'f ']. diisoquinoline-1,3,8,10-tetraone reacted and worked up. Y. 3.01 g (4.46 mmol, 88%) of a red, shiny metallic solid, mp> 300 ° C. IR (ATR): v ~ = 3471 (s), 2955 (s), 2929 (m), 2870 (m), 1688 (s), 1638 (s), 1592 (s), 1575 (s), 1444 ( m), 1403 (m), 1366 (m), 1339 (s), 1248 (m), 1149 (w), 1117 (w), 1052 (w), 1019 (m), 968 (w), 854 ( w), 811 (m), 793 (w), 752 cm ^-1 (w). ¹ H-NMR (600 MHz, CDCl ₃ ): δ = 0.92 (t, 12H, ³ J = 6.9 Hz, -CH ₃ ), 1.32 (m, 16H, -CH ₂ -), 3.22 (d, 4H, ³ J = 7.6 Hz, -CH ₂ -OH), 4.05 (t, 2H, ³ J = 7.6 Hz, -CH ₂ -OH), 4.21 (s, 4H, -CH ₂ -NR ₂ ), 8.68 (d, 4H , ³ J = 8.1 Hz, CH _ar ), 8.74 ppm (d, 4H, ³ J = 8.0 Hz, CH _ar ). UV / Vis (CHCl _3): λ _max (E _rel) = 528 (1.00) 492 (0.60), 460 nm (12:22). Fluorescence (CHCl ₃ ): λ _max = 536, 579 nm. MS (DEI ⁺ / 70 eV): m / z (%): 675 (29), 674 (54) [M ⁺ ], 644 (50) [M ⁺ -CH ₂ OH], 597 (67), 533 (21) [M ⁺ -C ₉ H ₁₈ OH], 404 (100), 390 (54) [M ⁺ -2 C ₉ H ₁₈ OH], 373 ( 22), 345 (22), 69 (32), 55 (22). HRMS (C ₄₂ H ₄₆ N ₂ O ₆ ): Ber. m / z: 674.3356, Gef. m / z: 674.3348, Δ = -0.8 mmu.

2,9-bis (2-butyl-2-hydroxymethylhexyl) anthra [2,1,9-def; 6,5,10-d'e'f '] diisoquinoline-1,3,8,10-tetrazone ( 7f) [7, 18]: perylene-3,4,9,10-tetracarboxylic acid 3,4: 9,10-bisanhydride (2.0 g, 5.1 mmol), 2-aminomethyl-2-butylhexan-1-ol (2.35 g, 12.5 mmol) and imidazole (16 g) were prepared analogously to 2,9-bis (2-ethyl-2-hydroxymethylbutyl) anthra [2,1,9-def; 6,5,10-d'e'f '] diisoquinoline-1,3,8,10-tetraone reacted and worked up. Y. 3.10 g (4.24 mmol, 83%) of a red solid with a slight metallic luster, mp> 300 ° C. IR (ATR): v ~ = 3455 (s), 2952 (s), 2862 (m), 1687 (s), 1639 (s), 1591 (s), 1575 (m), 1507 (w), 1444 ( m), 1403 m, 1368 w, 1337 s, 1245 m, 1219 w, 1184 w, 1147 w, 1118 w, 1050 w, 1024 m), 873 (w), 855 (w), 811 (w), 793 (w), 748 (w), 658 cm ^-1 (w). ¹ H-NMR (600 MHz, CDCl ₃ ): δ = 0.93 (t, 12H, ³ J = 7.1 Hz, -CH ₃ ), 1.32 (m, 24H, -CH ₂ -), 3.22 (d, 4H, ³ J = 7.6 Hz, -CH ₂ -OH), 4.04 (t, 2H, ³ J = 7.6 Hz, -CH ₂ -OH), 4.22 (s, 4H, -CH ₂ -NR ₂ ), 8.69 (d, 4H , ³ J = 8.1 Hz, CH _ar ), 8.74 ppm (d, 4H, ³ J = 8.0 Hz, CH _ar ). UV / Vis (CHCl _3): λ _max (E _rel) = 528 (1.00) 492 (0.60), 460 nm (12:23). Fluorescence (CHCl ₃ ): λ _max = 536, 579 nm.

2,9-bis (2-hydroxymethyl-2-pentylheptyl) anthra [2,1,9-def; 6,5,10-d'e'f '] diisoquinoline-1,3,8,10-tetrazone ( 7g) [18]: perylene-3,4,9,10-tetracarboxylic acid 3,4: 9,10-bisanhydride (2.0 g, 5.1 mmol), 2-aminomethyl-2-pentylheptyl-1-ol (2.53 g, 11.7 mmol) and imidazole (30 g) were prepared analogously to 2,9-bis (2-ethyl-2-hydroxymethylbutyl) anthra [2,1,9-def; 6,5,10-d'e'f ']. diisoquinoline-1,3,8,10-tetraone and worked up, boiled to dissolution with chloroform under reflux, precipitated after cooling with a little methanol, filtered off with suction, washed with methanol and dried in a drying oven at 90 ° C. Y. 3.72 g (93%) of red solid with strong metallic luster, mp 326-327 ° C. IR (ATR): v ~ = 3461 (m), 2956 (m), 2928 (m), 2860 (m), 1688 (s), 1639 (s), 1592 (m), 1575 (m), 1444 ( m), 1404 (m), 1368 (w), 1338 (s), 1254 (m), 1182 (w), 1119 (w), 1026 (m), 854 (w), 811 (m), 793 ( w), 747 (m), 659 cm ^-1 (w). ¹ H-NMR (600 MHz, CDCl ₃ ): δ = 0.90 (t, 12H, ³ J = 7.2 Hz, -CH ₃ ), 1.32 (m, 32H, -CH ₂ -), 3.22 (d, 4H, ³ J = 7.5 Hz, -CH ₂ -OH), 4:03 (t, 2H, ³ J = 7.5 Hz, -CH ₂ -OH), 4.21 (s, 4H, -CH ₂ -NR _2), 8.68 (d, 4H , ³ J = 8.1 Hz, CH _ar ), 8.73 ppm (d, 4H, ³ J = 8.0 Hz, CH _ar ). UV / Vis (CHCl _3): λ _max (E _rel) = 528 (1.00) 492 (0.60), 460 nm (12:22). Fluorescence (CHCl ₃ ): λ _max = 536, 579 nm. MS (DEI ⁺ / 70 eV): m / z (%): 788 (18) [M ⁺ ], 787 (57) [M ⁺ ], 786 ( 100) [M ⁺ ], 757 (50), 756 (93) [M ⁺ -CH ₂ OH], 589 (30) [M ⁺ -2 C ₁₃ H ₂₆ OH] 559 (15), 418 (40) 405 (63), 404 (98), 390 (58) [M ⁺ -2 C ₁₃ H ₂₆ OH].

2,9-bis (2-hydroxymethyl-2-octyldecyl) anthra [2,1,9-def; 6,5,10-d'e'f '] diisoquinoline-1,3,8,10-tetrazone ( 7h): perylene-3,4,9,10-tetracarboxylic acid 3,4: 9,10-bisanhydride (1.89 g, 4.82 mmol), 2-aminomethyl-2-pentylheptyl-1-ol (3.50 g, 11.1 mmol. ) and imidazole (50 g) were prepared analogously to 2,9-bis (2-ethyl-2-hydroxymethylbutyl) anthra [2,1,9-def; 6,5,10-d'e'f '] diisoquinoline. Reacted 1,3,8,10-tetraone and worked up and purified twice by chromatography (silica gel 60, chloroform / glacial acetic acid 10: 1). 1.27 g (63%) of a red solid, mp 293-296 ° C. R _f value (silica gel, CHCl ₃ / H ₃ CCO ₂ H 10: 1): 0.7. IR (ATR): v ~ = 3467 (s), 2957 (s), 2921 (s), 2852 (s), 1688 (s), 1640 (s), 1592 (s), 1575 (m), 1508 ( w), 1484 (vw), 1463 (w), 1443 (m), 1404 (m), 1392 (w), 1368 (w), 1339 (s), 1247 (m), 1200 (w), 1182 ( w), 1155 (w), 1120 (w), 1099 (w), 1066 (w), 1027 (m), 965 (w), 875 (w), 854 (w), 812 (m), 792 ( w), 748 (m), 720 cm ^-1 (w). ¹ H-NMR (600 MHz, CDCl ₃ ): δ = 0.88 (t, 12H, ³ J = 7.0 Hz, -CH ₃ ), 1.23-1.34 (m, 48H, -CH ₂ -), 1.40-1.47 (m , 4H, -CH ₂ -), 1.55 (m, 4H, -CH ₂ -), 3.21 (s, 2H, -CH ₂ -NR ₂ ), 4.02 (s, br, 2H, -OH), 4.20 (s , 4H, -CH ₂ -OH), 8.62 (d, 4H, ³ J = 8.0 Hz, CH _ar ), 8.69 ppm (d, 4H, ³ J = 7.9 Hz, CH _ar ). ¹³ C-NMR (600 MHz, CDCl _3): δ = 14.36 22.91, 23:19, 29.59, 29.80, 30.85, 32.13, 32.20, 43.30, 43.89, 65.92, 123.29, 133.56, 126.62, 129.56, 132.26, 135.05, 165.06 ppm , UV / Vis (CHCl _3): λ _max (ε) = 529 (88600), 492 (53300), 460 nm (19800 L · mol ^-1 · cm ^-1). Fluorescence (CHCl ₃ ): λ _max = 536, 579, 628 nm. Fluorescence quantum yield (CHCl ₃ , E = 0.0362, λ _exc = 490 nm, based on 7c) with Φ = 100%) = 100%. HRMS / ESI (C ₆₂ H ₈₆ N ₂ O ₆ ): Ber. m / z: 955.6486 [M ⁺ + H], Gef. m / z: 955.6556 [M ⁺ + H], Δ = 7 mmu. C ₆₂ H ₈₆ N ₂ O ₆ (955.4): Ber. C 77.95, H 9.07, N 2.93; Gef. C 78.02, H 9.14, N 2.95.

2,9-bis (2,3-dihydroxypropyl) anthra [2,1,9-def; 6,5,10-d'e'f '] diisoquinoline-1,3,8,10-tetrazone (7i) [31, 32, 33]: perylene-3,4,9,10-tetracarboxylic acid 3,4: 9,10-bisanhydride (2.0 g, 5.3 mmol), 3-aminopropane-1,2-diol (1.1 g, 12.1 mmol) and imidazole (15 g) were prepared analogously to 2,9-bis- (2-ethyl-2-hydroxymethylbutyl) anthra [2,1,9-def; 6,5,10-d'e'f ']. diisoquinoline-1,3,8,10-tetraone reacted and worked up. Y. 2.3 g (81%) brown-red powder. IR (ATR): v ~ = 3378 (br, s), 2955 (w), 1688 (s), 1653 (s), 1591 (vs), 1577 (m), 1508 (w), 1440 (m), 1404 (m), 1345 (s), 1246 (m), 1170 (m), 1112 (w), 1039 (m), 895 (w), 864 (w), 810 (m), 747 cm ^-1 ( m). UV / Vis (H ₂ SO _4): λ _max (ε) = 597 nm (70000), 556 (46300), 400 (10000 L · mol ^-1 · cm ^-1). Fluorescence (H ₂ SO ₄ ): λ _max = 623 nm. MS (DEI ⁺ / 70 eV) m / z (%): 539 (3) [M ⁺ ; Isotope 1], 538 (6) [M ⁺ ; Isotope 2], 523 (1) [M ⁺ -H ₂ O, isotope 1], 522 (2) [M ⁺ -H ₂ O, isotope 2], 521, (3), 520 (6), 508 (29 ) [M ⁺ -2 H ₂ O, isotope 1], 507 (100) [M ⁺ -2 H ₂ O, isotope 2], 465 (49) [M ⁺ -C ₃ H ₇ O ₂ ], 447 (32 ), 433 (46), 418 (33), 405 (30), 404 (74), 403 (34), 391 (49), 390 (73) [M ⁺ -2 C ₃ H ₇ O ₂ ], 376 (23), 345 (24), 43 (41). C ₃₀ H ₂₂ N ₂ O ₈ (538.5): Calcd. C 66.91, H 4.12, N 5.20; Gef. C 66.66, H 3.82, N 5.37.

N, N'-Quaterrylene-3,4,13,14-tetracarboxylic acid 3,4: 9,10-bis (1-hexylheptylimide) (13a) [34, 35, 36, 37]: 9,9'-bis - [perylene-3,4-dicarboxylic acid 3,4- (1-hexylheptylimd)] (200 mg, 196 mmol) was suspended with potassium carbonate (1.26 g, 9.31 mmol) in ethanolamine (1.8 mL), heated to 160 ° C , 4 h, allowed to cool to room temperature, with methanol (10 mL), filtered off, washed with plenty of distilled water, dried in a drying oven at 100 ° C for 16 h, chromatographed (silica gel, dichloromethane), taken up in a little dichloromethane with plenty of methanol felled and dried in a drying oven. Y. 96 mg (48%) of blue solid, mp> 250 ° C. R _f (silica gel / CH ₂ Cl ₂ ): 0.07. IR (ATR): v ~ = 2920 (s), 2851 (s), 1688 (s), 1645 (s), 1595 (m), 1571 (s), 1502 (m), 1456 1404 (m), 1372 (w), 1344 (s), 1284 (m) 1219 (w), 1171 (w), 1104 (w), 1047 (w), 836 (w) 804 (m), 745 (m), 669 cm ^{- 1} (w). ¹ H-NMR (CDCl _3, 600 MHz): δ = 0.85-0.95 (t, br, 12 H -CH _3), 1.14 (m, 32H, CH _2), 2:00 (m, br, 4H, NCH ₂ R -CH ₂ -R), 2.30 (m, 4H, R ₂ NCH-CH ₂ -R), 5.19 (m, 1H, R ₂ NCH-), 7.72-7.85 (m, 12H, CH _ar ), 8.23 ppm ( s, 4H, CH _ar ). ¹³ C-NMR (CDCl _3, 150 MHz): δ = 14.4, 2.9, 27.5, 29.6, 29.9, 31.2, 32.1, 32.7, 54.9, 120.4, 122.4, 123.8, 125.8, 127.3, 127.9, 129.2, 129.9, 131.3, 135.3, 164.8 ppm. UV / Vis: λ _max (E _rel) = 762 (1.00), 694, 377 nm (sh, 0:18.) (Sh, 0:09.). MS (ESI): m / z: 1002.5 [M ⁺ ].

2,7-bis (2-ethyl-2-hydroxymethylbutyl) -3,6,8-trioxo-1,2,3,6,7,8-hexahydro-benzo [lmn] [3,8] phenanthroline-1-ol Radical anion tetrabutylammonium salt (2a): 2,7-Bis (2-ethyl-2-hydroxymethylbutyl) benzo [lmn] [3,8] phenanthroline-1,3,6,8-tetraone (122 mg, 240 μmol) was added Argon, slurried with degassed ethanol (0.5 mL), and with degassed distilled water (1 mL) and DBU (1 mL), heated to 45 ° C, mixed with hydroxyacetone (1 mL, 15 mmol), stirred for 10 min, with tetrabutylammonium bromide (1.0 g, 3.1 mmol) in distilled water (1.5 g), diluted with degassed distilled water (10 mL), stirred for 10 min at 0 ° C, filtered under inert gas, washed with degassed distilled water until colorless, in a fine vacuum and then dried in a countercurrent nitrogen over phosphorus pentoxide. Y. 38 mg (21%) of a black-brown solid, mp> 300 ° C. IR (ATR): v ~ = 3332 (m, br), 2959 (s), 2875 (m), 1632 (s), 1580 (s), 1558 (s), 1520 (s), 1458 (m), 1376 (m), 1298 (m), 1146 (w), 1068 (m), 876 (w), 798 (w), 756 (w) cm ^-1 . UV / Vis (acetone): λ _max (E _rel ) = 477 nm (1.00), 611 (0.24), 686 (0.06), 761 (0.14).

2,7-bis (2-hydroxymethyl-2-propylpentyl) -3,6,8-trioxo-1,2,3,6,7,8-hexahydro-benzo [lmn] [3,8] phenanthroline-1-ol Radical Anion Tetrabutylammonium Salt (2b): 2,7-Bis- (2-hydroxymethyl-2-propylpentyl) benzo [lmn] [3,8] phenanthroline-1,3,6,8-tetraone (1b, 132 mg, 0.24 mmol) was analogously to 2,7-bis (2-ethyl-2-hydroxymethylbutyl) -3,6,8-trioxo-1,2,3,6,7,8-hexahydrobenzo [lmn] [3,8] phenanthroline Reacted and worked up 1-ol-Radikalaniontetrabutylammoniumsalz (2a). Y. 97 mg (0.11 mmol, 48%) of a black-brown solid, mp> 300 ° C. IR (ATR): v ~ = 3317 (m, br), 2958 (s), 2931 (m), 2872 (s), 1621 (s), 1577 (s), 1555 (m), 1516 (s), 1488 (w), 1461 (m), 1435 (w), 1379 (w), 1324 (m), 1296 (m), 1232 (w), 1204 (w), 1150 (w), 1103 (w), 1053 (w), 1010 (w), 880 (w), 853 (w), 812 (w), 744 cm ^-1 (w). ¹ H-NMR (400 MHz, D ₆ acetone): δ = 0.97 (t, 12H, ³ J = 7 Hz, R ₃ N- (CH ₂ ) ₃ -CH ₃ ), 1.42 (m, 8H, R ₃ N- (CH ₂ ) ₂ -CH ₂ -CH ₃ ), 1.80 (q, br, 8H, R ₃ N-CH ₂ -CH ₂ -CH ₂ -CH ₃ ), 3.42 ppm (t, 8H, ³ J = 8 Hz, R ₃ N-CH ₂ - (CH ₂ ) ₂ -CH ₃ ). ESR (solids): g = 2.0043. ESR (acetone): g = 2.0042. UV / Vis (acetone): λ _max (E _rel ) = 477 nm (1.00), 611 (0.13), 686 (0.08), 761 (0.02). MS (FAB ^- ): m / z (%): 550.3 (100) [M ^.- (C ₃₂ H ₄₂ N ₂ O ₆ ^.- )]. HRMS (C ₃₂ H ₄₂ N ₂ O ₆ ^.- ): Ber. 550.3048, Gef. 550.3063, Δ = 1.5 mmu.

2,7-bis (2-butyl-2-hydroxymethylhexyl) -3,6,8-trioxo-1,2,3,6,7,8-hexahydro-benzo [lmn] [3,8] phenanthroline-1-ol radical anion tetrabutylammonium salt (2c): 2,7-bis (2-butyl-2-hydroxymethylhexyl) benzo [lmn] [3,8] phenanthroline-1,3,6,8-tetraone (1c, 146 mg, 0.24 mmol) was analogously to 2,7-bis (2-ethyl-2-hydroxymethylbutyl) -3,6,8-trioxo-1,2,3,6,7,8-hexahydrobenzo [lmn] [3,8] phenanthroline 1-ol radikalaniontetrabu Tylammonium salt (2a) reacted and worked up. Y. 117 mg (58%) black-brown powder, mp> 300 ° C. IR (ATR): v ~ = 3300 (m, br), 3110 (m, br), 2956 (s), 2929 (s), 2872 (s), 1621 (s), 1587 (w), 1572 (w ), 1556 (m), 1523 (s), 1493 (w), 1463 (m), 1424 (w), 1400 (w), 1380 (w), 1364 (w), 1293 (m), 1196 (w ), 1145 (w), 1106 (w), 1066 (w), 1053 (w), 1026 (w), 984 (w), 935 (w), 879 (w), 815 (w), 743 cm ^{- 1} (w). ¹ H-NMR (400 MHz, D ₆ acetone): δ = 0.98 (t, 12H, ³ J = 7 Hz, R ₃ N- (CH ₂ ) ₃ -CH ₃ ), 1.43 (m, 8H, R ₃ N- (CH ₂ ) ₂ -CH ₂ -CH ₃ ), 1.82 (q, br, 8H, R ₃ N-CH ₂ -CH ₂ -CH ₂ -CH ₃ ), 3.46 ppm (t, 8H, ³ J = 8 Hz, R ₃ N-CH ₂ - (CH ₂ ) ₂ -CH ₃ ). ESR (acetone): g = 2.0039. UV / Vis (acetone): λ _max (E _rel ) = 477 nm (1.00), 611 (0.28), 686 (0.11), 761 (0.18). MS (FAB ^- ): m / z (%): 606.4 (100) [M ^.- (C ₃₆ H ₅₀ N ₂ O ₆ ^.- )]. HRMS (C ₃₆ H ₅₀ N ₂ O ₆ ^.- ): Ber. 606.3674, Gef. 606.3658, Δ = -1.6 mmu.

2,7-bis (2-hydroxymethyl-2-pentylheptyl) -3,6,8-trioxo-1,2,3,6,7,8-hexahydro-benzo [lmn] [3,8] phenanthroline-1-ol radical anion tetrabutylammonium salt (2d): 2,7-bis (2-hydroxymethyl-2-pentylheptyl) benzo [lmn] [3,8] phenanthroline-1,3,6,8-tetraone (1d, 159 mg, 0.24 mmol) was analogously to 2,7-bis (2-ethyl-2-hydroxymethylbutyl) -3,6,8-trioxo-1,2,3,6,7,8-hexahydrobenzo [lmn] [3,8] phenanthroline Reacted and worked up 1-ol-Radikalaniontetrabutylammoniumsalz (2a). Y. 207 mg (95%) of a black-brown solid, mp> 300 ° C. IR (ATR): v ~ = 3332 (m, br), 2956 (s), 2930 (m), 2871 (s), 1623 (s), 1586 (s), 1556 (m), 1519 (m), 1487 (w), 1464 (m), 1424 (w), 1400 (w), 1380 (w), 1365 (w), 1298 (m), 1256 (w), 1237 (w), 1189 (w), 1171 (w), 1141 (w), 1089 (w), 1057 (w), 1029 (w), 1012 (w), 979 (w), 958 (w), 932 (w), 879 (w), 833 (w), 812 (w), 759 (w), 739 cm ^-1 (w). ¹ H-NMR (400 MHz, D ₆ acetone): δ = 0.98 (t, 12H, ³ J = 7 Hz, R ₃ N- (CH ₂ ) ₃ -CH ₃ ), 1.43 (m, 8H, R ₃ N- (CH ₂ ) ₂ -CH ₂ -CH ₃ ), 1.83 (q, br, 8H, R ₃ N-CH ₂ -CH ₂ -CH ₂ -CH ₃ ), 3.45 ppm (t, 8H, ³ J = 8 Hz, R ₃ N-CH ₂ - (CH ₂ ) ₂ -CH ₃ ). ESR (acetone): g = 2.0040. UV / Vis (acetone): λ _max (E _rel ) = 477 nm (1.00), 611 (0.55), 686 (0.46), 761 (0.51). MS (FAB ^- ): m / z (%): 662.4 (100) [M ^.- (C ₄₀ H ₅₈ N ₂ O ₆ ^.- )]. HRMS (C ₄₀ H ₅₈ N ₂ O ₆ ^.- ): Ber. 662.4300, Gef. 662.4233. Δ = -6.7 mmu.

N, N'-bis (1-hexylheptyl) -N '' - (2-hydroxymethyl-2-octyldecyl) benzoperylene-1 ', 2': 3,4: 9,10-hexacarboxylic acid-1 ', 2' : 3,4: 9,10-tris (dicarboximide) radical anion tetrabutylammonium salt (5a): Dye 4a (47 mg, 42 μmol) was prepared analogously to 2,7-bis- (2-ethyl-2-hydroxymethylbutyl) - Reacted and worked up 3,6,8-trioxo-1,2,3,6,7,8-hexahydrobenzo [lmn] [3,8] -phenanthrolin-1-ol radical aniono-tetrabutylammonium salt (2a). Y. 38 mg green solid. UV / Vis (acetone): λ _max (E _rel ) = 646 (1.00), 721 (0.59), 863 nm (0.88).

N, N'-di (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic acid radical radical tetrabutylammonium salt (8c): N, N'-di- (1-hexylheptyl) -perylene-3,4: 9, 10-tetracarboxylic bisimide (7c, 0.18 g, 0.24 mmol) was prepared analogously to 2,9-bis (2-ethyl-2-hydroxymethylbutyl) anthra [2,1,9-def; 6,5,10d'e'f ' ] diisoquinoline-1,3,8,10-tetrazone radical anion tetrabutylammonium salt (2a) was reacted and worked up. Y. 197 mg (197 μmol, 82%) violet solid. IR (ATR): v ~ = 2958 cm ^-1 (s), 2924 (vs), 2856 (s), 1582 (vs), 1561 (s), 1524 (s), 1489 (s), 1362 (m) , 1318 (s), 1228 (w), 1132 (w), 1100 (w), 782 (w), 742 cm ^-1 (w). UV / Vis (acetone): λ _max (E _rel ) = 680 nm (0.61), 700 (1.00), 711 (0.92), 766 (0.37), 796 (0.60), 957 (0.43). ESR (acetone): g = 2.0037. ESR (solid state): g = 2.0041. MS (FAB ^- ): m / z: 754 (20) [M ^- (C ₅₀ H ₆₂ N ₂ O ₄ ^.- )]. HRMS (C ₅₀ H ₆₂ N ₂ O ₄ ^.- ): Ber: 754.4715, Gef. 754.4756, Δ = 0.5 mmu

2,9-bis (2-ethyl-2-hydroxymethylbutyl) anthra [2,1,9-def; 6,5,10d'e'f '] diisoquinoline-1,3,8,10-tetrazone radical anion tetrabutylammonium salt (8d) : 2,9-bis (2-ethyl-2-hydroxymethylbutyl) anthra [2,1,9-def; 6,5,10d'e'f '] diisoquinoline 1,3,8,10-tetrazone (7d, 148 mg, 239 μmol) was placed under argon, slurried with degassed ethanol (0.5 mL), and degassed with distilled water (1 mL) and 30 percent strength. NaOH (1 mL), heated to 50-55 ° C, treated with hydroxyacetone (1 mL, 15 mmol), stirred for 10 min, with tetrabutylammonium bromide (1.0 g, 3.1 mmol) in distilled water (1.5 g), with degassed diluted distilled water (10 mL), stirred for 10 min at 0 ° C, filtered under suction with suction, dried in a fine vacuum and then in a countercurrent nitrogen over phosphorus pentoxide. Y. 242 mg of violet powder; M.p.> 300 ° C. IR (ATR): v ~ = 3228 (br, m), 1600 (s), 1560 (m), 1541 (s), 1491 (m), 1468 (m), 1437 (m), 1415 (m), 1378 (m), 1358 (m), 1327 (s), 1297 (w), 1228 (m), 1208 (w), 1177 (w), 1145 (m), 1087 (w), 1051 (w), 999 (w), 968 (w), 928 (w), 875 (w), 820 (w), 788 (s), 752 (w), 735 (w), 700 (w), 632 (w), 579 cm ^-1 (w). ¹ H-NMR (400 MHz, D ₆ acetone): δ = 0.97 (t, 12H, ³ J = 7.3 Hz, N- (CH ₂ ) ₃ -CH ₃ ) 1.37-1.46 (m, 8H, ³ J = 7.3 Hz, 7.2 Hz, N- (CH ₂ ) ₂ -CH ₂ -CH ₃ ), 1.80 (m, br, 8H, N-CH ₂ -CH ₂ -CH ₂ -CH ₃ ), 3.41-3.45 ppm (t , 8H, ³ J = 7.7 Hz N-CH ₂ -CH ₂ -CH ₂ -CH _3). ESR (acetone): g = 2.0038. UV / Vis (acetone): λ _max (ε) = 680 (40,000), 702 (60,000), 711 (60,000), 767 (20,000), 797 (40,000), 957 nm (20,000 L · mol ^-1 cm ^-1) ). MS (FAB ^- ): m / z (%): 618.3 (100) [C ₃₈ H ₃₈ N ₂ O ₆ ^.- ]. HRMS (C ₃₈ H ₃₈ N ₂ O ₆ ^.- ): Ber. m / z: 618.2735, Gef. m / z: 618.2730, Δ = -0.5 mmu.

2,9-bis (2-hydroxymethyl-2-propylpentyl) anthra [2,1,9-def; 6,5,10d'e'f '] diisoquinoline-1,3,8,10-tetrazone radical anion tetrabutylammonium salt (8e) : 2,9-bis (2-hydroxymethyl-2-propylpentyl) anthra [2,1,9-def; 6,5,10d'e'f '] diisoquinoline 1,3,8,10-tetraone (7e, 164 mg, 243 μmol) was prepared analogously to 2,9-bis (2-ethyl-2-hydroxymethylbutyl) anthra [2,1,9-def; 6,5,10d'e'f '] diisoquinoline-1,3, Reacted and worked up 8,10-Tetraonradikalaniontetrabutylammonium salt (8d). Y. 254 mg purple festival fabric, m.p.> 300 ° C. IR (ATR): v ~ = 3525 (w), 3257 (br, m), 2957 (s), 2932 (s), 2872 (m), 1601 (s), 1542 (s), 1492 (m), 1466 (m), 1436 (w), 1414 (w), 1379 (w), 1359 (m), 1328 (s), 1294 (m), 1226 (m), 1208 (vw), 1177 (vw), 1145 (m), 1103 (w), 1081 (vw), 1057 (m), 1016 (vw), 955 (vw), 928 (w), 879 (w), 850 (vw), 788 (m), 744 (m), 701 cm ^-1 (m). ¹ H-NMR (400 MHz, D ₆ -acetone): δ = 0.97 (t, 12H, N- (CH ₂ ) ₃ -CH ₃ ), 1.39-1.43 (m, br, 8H, N- (CH ₂ ) ₂ -CH ₂ -CH ₃ ), 1.77-1.82 (m, br, 8H, N-CH ₂ -CH ₂ -CH ₂ -CH ₃ ), 3.41-3.45 ppm (m, br, 8H, N-CH ₂ - CH ₂ -CH ₂ -CH ₃ ). ESR (solid state): g = 2.0041. ESR (acetone): g = 2.0038. UV / Vis (acetone): λ _max (ε) = 680 (40,000), 702 (60,000), 711 (60,000), 767 (20,000), 797 (40,000), 957 nm (20,000 L · mol ^-1 cm ^-1) ). MS (-p ESI): m / z: 674 (100) [M ^- (C ₄₂ H ₄₆ N ₂ O ₆ ^.- )]. (+ p ESI): m / z: 243 (100) [C ₁₆ H ₃₆ N ⁺ ]. HRMS (C ₄₂ H ₄₆ N ₂ O ₆ ^.- ): Ber. m / z: 674.3361, Gef. m / z 674.3359, Δ = -0.2 mmu, (C ₁₆ H ₃₆ N ⁺ ): Ber. m / z: 242.2842, Gef. m / z: 242.2839, Δ = -0.3 mmu.

2,9-bis (2-hydroxymethyl-2-propylpentyl) anthra [2,1,9-def; 6,5,10d'e'f '] diisoquinoline-1,3,8,10-tetrazone radical anion tetrabutylammonium salt (8e) ; Precipitation of the radical anion with tetrabutylammonium hydrogensulfate: 2,9-bis (2-hydroxymethyl-2-propylpentyl) -anthra [2,1,9-def; 6,5,10d'e'f '] diisoquinoline 1,3,8,10 tetrazone (7e, 164 mg, 243 μmol) was added to 2,9-bis- (2-ethyl-2-hydroxymethylbutyl) anthra [2,1,9-def; 6,5,10d'e'f '] diisoquinoline-1,3,8,10-tetrazone radical anion tetrabutylammonium salt (8d) reacted and worked up; the precipitation was carried out with tetrabutylammonium hydrogen sulfate (1.1 g, 3.1 mmol in 1.5 mL degassed water). Y. 254 mg violet solid. IR (ATR): v ~ = 3525 cm ^-1 (w), 3257 (br, m), 2957 (s), 2932 (s), 2872 (m), 1601 (s), 1542 (s), 1492 ( m), 1466 (m), 1436 (w), 1414 (w), 1379 (w), 1359 (m), 1328 (s), 1294 (m), 1226 (m), 1208 (vw), 1177 ( vw), 1145 (m), 1103 (w), 1081 (vw), 1057 (m), 1016 (vw), 955 (vw), 928 (w), 879 (w), 850 (vw), 788 ( m), 744 (m), 701 (m). UV / Vis (acetone): λ _max (ε) = 680 (40,000), 702 (60,000), 711 (60,000), 767 (20,000), 797 (40,000), 957 nm (20,000 L · mol ^-1 cm ^-1) ).

2,9-bis (2-hydroxymethyl-2-butyloctyl) anthra [2,1,9-def; 6,5,10d'e'f '] diisoquinoline-1,3,8,10-tetrazone radical anion tetrabutylammonium salt (8f) : 2,9-bis (2-hydroxymethyl-2-butyloctyl) anthra [2,1,9-def; 6,5,10d'e'f '] diisoquinoline 1,3,8,10-tetraone (7f, 177 mg, 242 μmol) was prepared analogously to 2,9-bis (2-ethyl-2-hydroxymethylbutyl) anthra [2,1,9-def; 6,5,10d'e'f '] diisoquinoline-1,3, Reacted and worked up 8,10-Tetraonradikalaniontetrabutylammonium salt (8d). Y. 277 mg violet solid, mp> 300 ° C. IR (ATR): v ~ = 3236 (br, m), 2957 (s), 2930 (s), 2871 (m), 1600 (s), 1541 (s), 1492 (m), 1466 (m), 1436 (w), 1413 (w), 1378 (w), 1359 (m), 1328 (s), 1296 (m), 1229 (m), 1208 (w), 1177 (vw), 1145 (m), 1104 (w), 1086 (vw), 1053 (m), 935 (w), 876 (w), 795 (m), 788 (m), 742 (m) 702 (m) 647 cm ^-1 (w) , ¹ H-NMR (400 MHz, d ₆ -acetone): δ = 0.97 (t, 12H, -CH ₃ (C ₁₆ H ₃₆ N ⁺ )), 1.41-1.43 (m, br, 8H, -CH ₂ -CH ₃ (C ₁₆ H ₃₆ N ⁺ )), 1.80-1.82 (m, br, 8H, -CH ₂ -CH ₂ -CH ₃ (C ₁₆ H ₃₆ N ⁺ )), 3.45-3.46 ppm (t, br, 8H , -CH ₂ -N (C ₁₆ H ₃₆ N ⁺ )). ESR (acetone): g = 2.0037. UV / Vis (acetone): λ _max (E _rel) = 680 (0.62) 701 (0.98) 710 (1.00), 766 (0:26), 796 (00:57), 957 nm (12:36). MS (FAB ^- ): m / z (%): 730.4 (100) [M ^- (C ₄₆ H ₅₄ N ₂ O ₆ ^.- ). HRMS (C ₄₆ H ₅₄ N ₂ O ₆ ^.- ): Ber. m / z: 730.3987, Gef. m / z: 730.3982, Δ = -0.5 mmu.

2,9-Bis (2-hydroxymethyl-2-pentylheptyl) anthra [2,1,9-def; 6,5,10d'e'f '] diisoquinoline-1,3,8,10-tetrazone radical anion tetrabutylammonium salt (8g) : 2,9-bis (2-hydroxymethyl-2-pentylheptyl) anthra [2,1,9-def; 6,5,10d'e'f '] diisoquinoline 1,3,8,10-tetrazone (7g, 189 mg, 240 mmol) was analogously to 2,9-bis (2-ethyl-2-hydroxymethylbutyl) anthra [2,1,9-def; 6,5,10d'e'f '] diisoquinoline-1,3, Reacted and worked up 8,10-Tetraonradikalaniontetrabutylammonium salt (8d). Y. 346 mg violet solid, mp> 300 ° C. IR (ATR): v ~ = 3250 (br, m), 2955 (s), 2928 (s), 2871 (m), 1600 (s), 1561 (w), 1543 (s), 1488 (m), 1466 (m), 1377 (w), 1360 (m), 1330 (s), 1296 (m), 1229 (m), 1204 (vw), 1145 (m), 1105 (w), 1067 (m), 949 (vw), 878 (w), 788 (m), 741 (m), 702 (m), 646 cm ^-1 (w). ¹ H-NMR (400 MHz, d ₆ -acetone): δ = 0.98 (t, 12H, -CH ₃ (C ₁₆ H ₃₆ N ⁺ )), 1.40-1.46 (m, br, 8H, CH ₂ -CH ₃ (C ₁₆ H ₃₆ N ⁺ )), 1.82 (m, br, 8H, -CH ₂ -CH ₂ -CH ₃ (C ₁₆ H ₃₆ N ⁺ )), 3.47-3.48 ppm (t, br, 8H, -CH ₂ -N (C ₁₆ H ₃₆ N ⁺ )). ESR (acetone): g = 2.0037. UV / Vis (acetone): λ _max (E _rel ) = 956 nm (0.36), 796 (0.58), 766 (0.28), 711 (1.00), 701 (0.98), 680 (0.63). MS (-p ESI): m / z: 786 (50) [M ^- (C ₅₀ H ₆₂ N ₂ O ₆ ^.- )]. (p + ESI): m / z: 242 (100) [C ₁₆ H ₃₆ N ^+], HRMS (C ₅₀ H ₆₂ N ₂ O ₆ ^.-): Calcd. m / z: 786.4631, Gef. m / z 786.4607, Δ = -2.4 mmu, (C ₁₆ H ₃₆ N ⁺ ): Ber. m / z 242.2842, Gef. m / z 242.2838, Δ = -0.4 mmu.

2,9-bis (2-hydroxymethyl-2-octyldecyl) anthra [2,1,9-def; 6,5,10d'e'f '] diisoquinoline-1,3,8,10-tetrazone radical anion tetrabutylammonium salt (8h) : 2,9-bis (2-hydroxymethyl-2-octyldecyl) anthra [2,1,9-def; 6,5,10d'e'f '] diisoquinoline 1,3,8,10-tetraone (7h, 229 mg, 240 μmol) was prepared analogously to 2,9-bis (2-ethyl-2-hydroxymethylbutyl) anthra [2,1,9-def; 6,5,10d'e'f '] diisoquinoline-1,3, Reacted and worked up 8,10-Tetraonradikalaniontetrabutylammonium salt (8d). Y. 294 mg violet solid, mp 230 ° C. IR (ATR): v ~ = 3449 (br, w), 3239 (br, w), 2957 (m), 2922 (s), 2852 (m), 1601 (s), 1541 (s), 1490 (m ), 1464 (m), 1439 (m), 1361 (w), 1329 (s), 1297 (m), 1228 (m), 1208 (w), 1176 (w), 1147 (m), 1096 (w ), 1054 (w), 1024 (w), 940 (w), 912 (w), 876 (w), 788 (s), 740 (s), 724 (w), 703 (m), 648 cm ^{- 1} (w). ESR (acetone): g = 2.0038. UV / Vis (acetone): λ _max (E _rel ) = 957 nm (0.48), 797 (0.63), 767 (0.29), 711 (1.00), 701 (0.97), 680 (0.61). MS (FAB ^- ): m / z (%): 954.7 (100) [M ^- (C ₆₂ N ₈₆ N ₂ O ₆ ^.- )] HRMS (C ₆₂ H ₈₆ N ₂ O ₆ ^.- ): Calcd. m / z: 954.6491, Gef. m / z: 954.6486, Δ = -0.5 mmu.

N, N'-quaterrylene-3,4,13,14-tetracarboxylic acid 3,4: 9,10-bis (1-hexylheptylimide) radical anionotetrabutylammonium salt (14a): quaterrylene-3,4,13,14-tetracarboxylic acid-3, 4: 9,10-bis (1-hexylheptylimide) (13a, 50 mg, 50 μmol) was analogous to 2,7-bis (2-ethyl-2-hydroxymethylbutyl) -3,6,8-trioxo-1, 2,3,6,7,8-hexahydrobenzo [lmn] [3,8] phenanthrolin-1-ol radical anionic tetrabutylammonium salt (2a) was reacted and worked up. Y. 63 mg green solid. IR (ATR): v ~ = 2957 (m), 2924 (m), 2855 (m), 1643 (m), 1564 (s), 1532 (m), 1504 (m), 1480 (w), 1465 ( m), 1376 (m), 1364 (m), 1332 (s), 1292 (w), 1277 (w), 1242 (s), 1203 (w), 1180 (w), 1144 (w), 1104 ( w), 1048 (w), 937 (w), 883 (w), 806 (w), 780 (m), 748 (m), 664 (w), 608 (w), 588 cm ^-1 (w) , UV / Vis (acetone): λ _max = 1075 (1.00), 1185 (0.16), 1251 (0.30), 1697 nm (0.20). MS (FAB ^-): m / z: 1002.5 (100) [M ^- (C ₇₀ H ₇₀ N ₂ O ₄ ^.-)], HRMS (C ₇₀ H ₇ N ₂ O ₄ ^.-): Calcd. 1002.5341, Gef. 1002.5372, Δ = 3.1 mmu.

vATTING and direct UV / Vis spectroscopic measurement, Example 1b: N, N'-di- (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic bisimide 1b (1.0 mg, 1.3 μmol) is verküpt according to 2a or 8d. Instead of the precipitation becomes a defined small amount of the vat under inert gas to a measuring solution given, consisting from DBU (0.8 mL, 8 mmol), hydroxyacetone (0.5 mL, 7 mmol) and diacetyl (1 mL, 11 mmol) dissolved in a little acetone (Uvasol) and then quickly filled with acetone (Uvasol) to 25 mL, and against the Measurement solution UV / Vis / NIR spectroscopically measured. If the Components of the measuring solution before filling too have long contact, then decomposition occurs under browning and thus falsification of the measurement results.

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Subject of the invention

• 1. Naphthalene bisimide radical anions of the general formula 16 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 6 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-disub 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-od he 9,10-disubstituted 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 the quaternary carbon atoms can be linked in pairs, so that rings are formed, such. B. cyclohexane rings. The radicals R ¹ to R ⁶ may also independently of one another denote the halogen atoms F, Cl, Br or I.
• 2. Naphthalene bisimide bisanions of the general formula 17 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 ^{6 have} the meaning given under 1.
• 3. perylenebisimide radical anions of the general formula 18 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 ^{6 have} the meaning given under 1.
• 4. Perylenbisimidanionen of the general formula 19 as salts, especially tetrabutylammonium salts, or as salts with other cations as counter ions 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 ^{6 have} the meaning given under 1.
• 5. Benzoerylentrisimidradikalanionen of the general formula 20 as salts, especially tetrabutylammonium salts, or as salts with other cations as counter ions 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 ^{5 have} the meaning given under 1.
• 6. Benzoerylentrisimidanionen of the general formula 21 as salts, especially tetrabutylammonium salts, or as salts with other cations as counter ions 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 ^{5 have} the meaning given under 1.
• 7. Terrylenbisimidradikalanionen of the general formula 22 as salts, especially tetrabutylammonium salts, or as salts with other cations as counter ions 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 6 have the meaning given under 1 and R 7 to R 10 have the meaning of R 1 to R 4 under 1.
• 8. Terrylenbisimidanionen of the general formula 23 as salts, especially tetrabutylammonium salts, or as salts with other cations as counter ions 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 6 have the meaning given under 1 and R 7 to R 10 have the meaning of R 1 to R 4 under 1.
• 9. Quaterrylenbisimidradikalanionen of the general formula 24 as salts, especially tetrabutylammonium salts, or as salts with other cations as counter ions 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 6 have the meaning given under 1 and R 7 to R 12 have the meaning of R 1 to R 6 under 1 and R 13 to R 14 have the meaning of R 1 to R 2 under 1.
• 10. Quaterrylenbisimidanionen of the general formula 25 as salts, especially tetrabutylammonium salts, or as salts with other cations as counter ions 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 6 have the meaning given under 1 and R 7 to R 12 have the meaning of R 1 to R 6 under 1 and R 13 to R 14 have the meaning of R 1 to R 2 under 1.
• 11. Dyes of the general formulas 16 to 25, according to claim 1-10, in which quaternary ammonium salts as countercations be used. Preference is given to quadruply alkylated ammonium salts, more preferred are ammonium salts in which four Alkyl groups present. These can be branched like iso-propyl groups its synthesis is conveniently one of the groups a benzyl group, or these may also be unbranched such as n-alkyl groups, most preferred is tetra-n-butylammonium.
• 12. Dyestuffs of the general formulas 16 to 25, according to claim 1-11, in which as Cationic counterions large-volume Ions are used. Examples of such counterions are cesium ions, potassium ions or quaternary phosphonium ions.
• 13. The method according to claim 1-12, characterized in that the anions and radical anions are synthesized according to 1 to 12 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 which form endiols or endiolates in alkaline solution, in particular low molecular weight compounds (C ₂ to C ₈ ) such as Hydroxyketones and α-hydroxy aldehydes such. Hydroxyacetone, dihydroxyacetone, glycolaldehyde, dihydroxybutanone, 2,3-dihydroxyacrylaldehyde (triose reductone), ascorbic acid or cyclopentendiol-on (reductic acid), preferably hydroxyacetone carbohydrates and other natural products having unsaturated bonds.
• 14. The method according to claim 1-12, characterized that the anions and radical anions after 1 to 12 by electrochemical Reduction of the corresponding bisimides can be synthesized. preferred Cathode materials are lead, tin, steel, stainless steel, aluminum, Copper and silver, carbon, especially graphite. Naturally Also, mercury and cadmium can be used characterized by a high overvoltage, but off Environmental reasons should be avoided. It will a temperature range of 10 to 60 ° C is preferred. preferably, The anode-electrolyte space is separated from the cathode compartment, so no re-oxidation of the dye radical anions takes place. This can be carried out by ion-selective membranes such. B. Nafion, or through diaphragms, such. B. sound diaphragms. Especially with the the latter, the anode compartment is preferably permanently purged.
• 15. The method according to claim 1-14, characterized that the anions and radical anions precipitate as salts according to 1 to 12 and processed further in this form. 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.
• 16. The method according to claim 1-12, characterized that the anions and radical anions according to 1 to 12 from the relevant Bisimides are reduced in alkaline solution. 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.
• 17. The method according to claim 1-12, characterized that dyes from the radical ions according to 1 to 12 by oxidizing agents be generated specifically. Preferred oxidizing agents are peroxides such as hydrogen peroxide and its various forms of storage such as urea inclusion compounds, Percarbonates, persulfates or perborates, as well as ozone, ultraviolet light, oxidative Processes in the anode compartment of a suitable electrolysis cell.
• 18. Application of the dyes according to claim 1-17 as vat dyes, for. B. for dyeing textiles, preferably textiles herbal Ur Like cotton or even preferably synthetic fibers such as polyester or nylon.
• 19. Use of the substances according to claim 1-17 or their oxidation products as pigments.
• 20. Use of the substances according to claim 1-17 or their oxidation products as pigments for distempers and related colors like watercolor paints and watercolors and colors for Inkjet Printers Paper inks, inks, inks and inks and other colors for painting and writing purposes and in paints.
• 21. Use of the substances according to claim 1-17 or their oxidation products as pigments in paints. Preferred paints are synthetic resin lacquers such as acrylic or vinyl resins, polyester lacquers, Novolaks, nitrocellulose lacquers (nitro lacquers) or natural substances like Zaponlack, shellac or Qi-Lack (Japanese lacquer or Chinese lacquer or East Asian lacquer).
• 22. Use of the dyes according to claim 1-17 or their oxidation products in data storage, preferably in optical To save. Examples are systems such as the CD or DVD disc.
• 23. Use of the substances according to claim 1-17 or their oxidation products as fluorescent dyes.
• 24. Application of the dyes of claim 1-17 or their oxidation products for mass-dyeing polymers. Examples are materials of polyvinyl chloride, cellulose acetate, polycarbonates, Polyamides, polyurethanes, polyimides, polybenzimidazoles, melamine resins, silicones, Polyesters, polyethers, polystyrene polymethylmethacrylate, polyethylene, Polypropylene, polyvinyl acetate, polyacrylonitrile, polybutadiene, polychlorobutadiene or polyisoprene or the copolymers of said monomers, and Alkyd resin and acrylic paints.
• 25. Application of the dyes according to claim 1-17 or their oxidation products as vat dyes, eg. B. for Coloring of natural substances. Examples are paper, wood, Straw, leather, skins or natural fiber materials like Cotton, wool, silk, jute, sisal, hemp, flax and their transformation products such as As the viscose fiber, nitrate silk or copper rayon (rayon).
• 26. Application of the dyes according to claim 1-17 or their oxidation products as mordant dyes, eg. For coloring of natural substances. Examples are paper, wood, straw, leather, skins or natural fiber materials such as cotton, wool, Silk, jute, sisal, hemp, flax and their transformation products such as z. As the viscose fiber, nitrate silk or copper rayon (rayon). Preferred salts For pickling are aluminum, chromium and iron salts.
• 27. Application of the dyes according to claim 1-17 or their oxidation products as colorants, for. For coloring paints, varnishes and other paints, paper inks, printing inks, Inks and other colors for painting, writing and coloring purposes all kinds.
• 28. Application of the dyes according to claim 1-17 or their oxidation products as pigments in electrophotography: z. B. for dry copying systems (Xerox process) and laser printers ("Non-Impact Printing").
• 29. Application of the dyes according to claim 1-17 or their oxidation products for safety marking purposes, being the great chemical and photochemical resistance and possibly also the fluorescence of the substances is of importance. This is preferred for checks, check cards, banknotes Coupons, documents, identity documents and the like, in which a special, unmistakable color impression is to be achieved.
• 30. Application of the dyes of claim 1-17 or their oxidation products as an additive to other colors, at which a certain color shade is to be achieved, are preferred particularly bright shades.
• 31. Application of the dyes of claim 1-17 or their oxidation products for marking objects for machine recognition of these objects the fluorescence, preferred is the machine detection of objects to sort, z. B. also for the recycling of plastics.
• 32. Application of the dyes of claim 1-17 or their oxidation products as fluorescent dyes for Machine-readable markings, preferred are alphanumeric imprints or barcodes.
• 33. Use of the dyes according to claim 1-17 or their oxidation products for the frequency conversion of light, z. B. from short-wave light, longer-wave, visible light close.
• 34. Application of the dyes of claim 1-17 or their oxidation products in display elements for many Display, hint and marking purposes, e.g. B. passive display elements, Signs and traffic signs, such as traffic lights.
• 35. Application of the dyes according to claim 1-17 or their oxidation products in inkjet printers in homogeneous solution as an ink or as a fluorescent ink.
• 36. Application of the dyes according to claim 1-17 or their oxidation products as a starting material for superconducting organic materials.
• 37. Application of the dyes according to claim 1-17 or their oxidation products for solid fluorescence labels.
• 38. Use of the dyes of claim 1-17 or their oxidation products for decorative purposes.
• 39. Application of the dyes according to claim 1-17 or their oxidation products for artistic purposes.
• 40. Use of the dyes according to claim 1-17 or their oxidation products for tracer purposes, eg. In biochemistry, Medicine, technology and science. Here, the Dyes be covalently linked to substrates or over Nebenvalenzen such as hydrogen bonds or hydrophobic Interactions (adsorption).
• 41. Application of the dyes according to claim 1-17 or their oxidation products as fluorescent dyes in highly sensitive Detection methods.
• 42. Application of the dyes according to claim 1-17 or their oxidation products as fluorescent dyes in scintillators.
• 43. Application of the dyes according to claim 1-17 or their oxidation products as dyes or fluorescent dyes in optical light collection systems.
• 44. Use of the dyes according to claim 1-17 or their oxidation products as dyes or fluorescent dyes in fluorescence solar collectors.
• 45. Application of the dyes according to claim 1-17 or their oxidation products as dyes or fluorescent dyes in fluorescence-activated displays.
• 46. Application of the dyes according to claim 1-17 or their oxidation products as dyes or fluorescent dyes in cold light sources for light-induced polymerization for illustration of plastics.
• 47. Application of the dyes according to claim 1-17 or their oxidation products as dyes or fluorescent dyes for material testing, z. B. in the manufacture of semiconductor circuits.
• 48. Use of the dyes according to claim 1-17 or their oxidation products as dyes or fluorescent dyes for the investigation of microstructures of integrated semiconductor devices.
• 49. Application of the dyes according to claim 1-17 or their oxidation products as dyes or fluorescent dyes in photoconductors.
• 50. Application of the dyes according to claim 1-17 or their oxidation products as dyes or fluorescent dyes in photographic processes.
• 51. Use of the dyes according to claim 1-17 or their oxidation products as dyes or fluorescent dyes in display, lighting or image converter systems in which the Excitation by electrons, ions or UV radiation takes place, for. B. in fluorescent displays, Braun tubes or in fluorescent tubes.
• 52. Application of the dyes according to claim 1-17 or their oxidation products as dyes or fluorescent dyes as part of a semiconductor integrated circuit, the dyes as such or in conjunction with other semiconductors z. B. in shape an epitaxy.
• 53. Application of the dyes according to claim 1-17 or their oxidation products as dyes or fluorescent dyes in chemiluminescent systems, e.g. In chemiluminescent light sticks, in luminescence immunoassays or other luminescence detection methods.
• 54. Application of the dyes according to claim 1-17 or their oxidation products as dyes or fluorescent dyes as signal colors, preferably for the visual highlighting of lettering and drawings or other graphic products, for marking of signs and other objects, where a special one optical color impression is to be achieved.
• 55. Application of the dyes according to claim 1-17 or their oxidation products as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for production of laser beams.
• 56. Application of the dyes according to claim 1-17 or their oxidation products as dyes in dye lasers as Q-switch switch.
• 57. Application of the dyes according to claim 1-17 or their oxidation products as active substances for a nonlinear optics, e.g. B. for frequency doubling and the frequency tripling of laser light.
• 58. Application of the dyes according to claim 1-175 or their oxidation products for leak testing closed Systems.
• 59. Application of the dyes according to claim 1-17 or their oxidation products as Rheologieverbesserer.
• 60. Application of the dyes according to claim 1-17 to Oak of spectrometers, preferably ESR spectrometer (electron spin resonance).
• 61. Use of the dyes according to claims 1-17 as NIR dyes.
• 62. Application of the dyes according to claim 1-17 as Thermal protection dyes.
• 63. Application of the dyes according to claims 1-17 as light-absorbing substances in thermal solar collectors.
• 64. Use of the dyes according to claims 1-17 in the plastic layer of laminated glass, preferably as protection against NIR radiation and this is preferred in the automotive industry.
• 65. Use of the dyes according to claim 1-17 for promoting the evaporation of water in salines, preferably embedded in plastic parts and here preferably embedded in art fabric balls, and here preferably the mentioned under 24 plastic materials.

LIST OF REFERENCE NUMBERS

1 , Synthesis of naphthalene bisimide radical anions (2) and further reaction to the bisanions 3.

2 , UV / Vis absorption spectrum of 2b in acetone.

3 , Solid UV / Vis / NIR absorption spectrum of 2b.

4 , Benzoperylenhexacarboxylic trisimides 4, their radical anion 5 and bisanions 6.

5 , Peryletetracarboxylic bisimides 7, their radical anions 8 and bisanions 9.

6 , UV / Vis Absorption spectrum of the vesicle of 7e (left) in acetone with predominant formation of bisanion 9e and spectrum upon addition of diacetyl (right) with predominant formation of radical anion 8e.

7 , UV / Vis Absorption spectrum of the vat of 7i (left) in acetone with predominant formation of bisanion 9i and spectrum upon addition of diacetyl (right) with predominant formation of radical anion 8i.

8th , ESR spectrum of the radical 8e in acetone (left) and as a solid (right).

9 , UV / Vis absorption spectrum of the precipitated and redissolved radical anion 7e in acetonitrile.

10 , Terryletetracarbonsäurebisimide 10, their radical anions 11 and bisanions 12.

11 , Terrylenbisimid 10a in chloroform (left), vat of Terrylenbisimids in acetone (center) with predominant formation of bisanion 13a and vat of Terrylenbisimids in acetone after addition of diacetyl (right) with predominant formation of the radical anion 12a.

12 , Quaterryletetracarboxylic bisimides 13, their radical anions 14 and bisanions 15.

13 , Quaterrylenebisimide 13a in chloroform (left), vat of quaterrylene bisimide in acetone (right) with predominant formation of bisanion 15a.

14 , Quaterrylenebisimide 13a in chloroform (left), vat of the terrylenebisimide in acetone after addition of diacetyl (right) with predominant formation of the radical anion 14a.

15 , UV / Vis spectrum of the isolated quaterrylenebisimide radical 14a in acetone.

16 , Comparison of the longest wavelength UV / Vis absorption spectra of naphthalene bisimides 1, benzoperylene trisimides 4, perylene 7, terrylene 10 and quaterrylene bisimides 13 (left scale, chloroform) With those of their radical anions 3, 5, 8, 11 and 14 (right scale, acetone) ,

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

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Claims (65)

Naphthalene bisimide radical anions of the general formula 16 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 6 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-disub 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-od he 9,10-disubstituted 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 the quaternary carbon atoms can be linked in pairs, so that rings are formed, such. B. cyclohexane rings. The radicals R ¹ to R ⁶ may also independently of one another denote the halogen atoms F, Cl, Br or I. Naphthalene bisimide bisanions of general formula 17 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 ^{6 have} the meaning given under 1. Perylenebisimide radical anions of the general formula 18 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 ^{6 have} the meaning given under 1. Perylenbisimidanionen the general formula 19 as salts, especially 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 Trialkylammoniumsalze or even H ⁺ , H ₃ O ⁺ or other hydrated protons or protonated forms,

in which the radicals R ¹ to R ^{6 have} the meaning given under 1. Benzoerylentrisimidradikalanionen the general formula 20 as salts, especially 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 Trialkylammoniumsalze or even H ⁺ , H ₃ O ⁺ or other hydrated protons or protonated forms,

in which the radicals R ¹ to R ^{5 have} the meaning given under 1. Benzoerylentrisimidanionen the general formula 21 as salts, especially 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 Trialkylammoniumsalze or even H ⁺ , H ₃ O ⁺ or other hydrated protons or protonated forms,

in which the radicals R ¹ to R ^{5 have} the meaning given under 1. Terrylenbisimidradikalanionen the general formula 22 as salts, especially 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 Trialkylammoniumsalze or even H ⁺ , H ₃ O ⁺ or other hydrated protons or protonated forms,

in which the radicals R 1 to R 6 have the meaning given under 1 and R 7 to R 10 have the meaning of R 1 to R 4 under 1. Terrylenbisimidanionen the general formula 23 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 Trialkylammoniumsalze or even H ⁺ , H ₃ O ⁺ or other hydrated protons or protonated forms,

in which the radicals R 1 to R 6 have the meaning given under 1 and R 7 to R 10 have the meaning of R 1 to R 4 under 1. Quaterrylenbisimidradikalanionen of the general formula 24 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 Trialkylammoniumsalze or even H ⁺ , H ₃ O ⁺ or other hydrated protons or protonated forms,

in which the radicals R 1 to R 6 have the meaning given under 1 and R 7 to R 12 have the meaning of R 1 to R 6 under 1 and R 13 to R 14 have the meaning of R 1 to R 2 under 1. Quaterrylenbisimidanionen the general formula 25 as salts, especially 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 Trialkylammoniumsalze or even H ⁺ , H ₃ O ⁺ or other hydrated protons or protonated forms,

in which the radicals R 1 to R 6 have the meaning given under 1 and R 7 to R 12 have the meaning of R 1 to R 6 under 1 and R 13 to R 14 have the meaning of R 1 to R 2 under 1. Dyes of the general formulas 16 to 25, according to Claims 1-10, in which quaternary ammonium salts used as counter cations. Preference is given to quadruply alkylated Ammonium salts, more preferred are ammonium salts, where four alkyl groups are present. These can be branched such as iso-propyl groups, then their synthesis is conveniently one of the groups is a benzyl group, or these may be too be unbranched such as n-alkyl groups, most preferably tetra-n-butylammonium. Dyes of the general formulas 16 to 25, according to Claims 1-11, in which large-volume as cationic counterions Ions are used. Examples of such counterions are cesium ions, potassium ions or quaternary phosphonium ions. A method according to claim 1-12, characterized in that the anions and radical anions are synthesized according to 1 to 12 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 which form endiols or endiolates in alkaline solution, in particular low molecular weight compounds (C ₂ to C ₈ ) such as Hydroxyketones and α-hydroxy aldehydes such. Hydroxyacetone, dihydroxyacetone, glycolaldehyde, dihydroxybutanone, 2,3-dihydroxyacrylaldehyde (triose reductone), ascorbic acid or cyclopentendiol-on (reductic acid), preferably hydroxyacetone carbohydrates and other natural products having unsaturated bonds. Method according to claims 1-12, characterized in that that the anions and radical anions after 1 to 12 by electrochemical Reduction of the corresponding bisimides can be synthesized. preferred Cathode materials are lead, tin, steel, stainless steel, aluminum, Copper and silver, carbon, especially graphite. Naturally Also, mercury and cadmium can be used characterized by a high overvoltage, but off Environmental reasons should be avoided. It will a temperature range of 10 to 60 ° C is preferred. preferably, The anode-electrolyte space is separated from the cathode compartment, so no re-oxidation of the dye radical anions takes place. This can be carried out by ion-selective membranes such. B. Nafion, or through diaphragms, such. B. sound diaphragms. Especially with the the latter, the anode compartment is preferably permanently purged. Method according to claims 1-14, characterized that the anions and radical anions precipitate as salts according to 1 to 12 and processed further in this form. 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 1-12, characterized in that that the anions and radical anions according to 1 to 12 from the relevant Bisimides are reduced in alkaline solution. 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), on Most preferred is DBU. Method according to claims 1-12, characterized in that that dyes from the radical ions according to 1 to 12 by oxidizing agents be generated specifically. Preferred oxidizing agents are peroxides such as Hydrogen peroxide and its various forms of storage such as urea inclusion compounds, Percarbonates, persulfates or perborates, as well as ozone, ultraviolet light, oxidative Processes in the anode compartment of a suitable electrolysis cell. Application of the dyes according to claim 1-17 as vat dyes, for. B. for coloring Tex tilien, preferably textiles of plant origin such as cotton or else preferably synthetic fibers such as polyester or nylon. Use of the substances according to claims 1-17 or their oxidation products as pigments. Use of the substances according to claims 1-17 or their oxidation products as pigments for distempers and related colors such as watercolor paints and watercolors and colors for inkjet printers paper inks, inks, inks and ink and other colors for painting and writing purposes and in paints. Use of the substances according to claims 1-17 or their oxidation products as pigments in paints. preferred Paints are synthetic resin varnishes such as acrylic or vinyl resins, polyester varnishes, Novolaks, nitrocellulose lacquers (nitro lacquers) or natural substances like Zaponlack, shellac or Qi-Lack (Japanese lacquer or Chinese lacquer or East Asian lacquer). Use of the dyes according to claims 1-17 or their oxidation products in data storage, preferably in optical To save. Examples are systems such as the CD or DVD disc. Use of the substances according to claims 1-17 or their oxidation products as fluorescent dyes. Application of the dyes of claim 1-17 or their oxidation products for mass-dyeing polymers. Examples are materials of polyvinyl chloride, cellulose acetate, Polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, Melamine resins, silicones, polyesters, polyethers, polystyrene polymethylmethacrylate, Polyethylene, polypropylene, polyvinyl acetate, polyacrylonitrile, polybutadiene, Polychlorobutadiene or polyisoprene or the copolymers of said monomers, as well as alkyd resin and acrylic paints. Application of the dyes according to claims 1-17 or their oxidation products as vat dyes, eg. B. for coloring natural substances. Examples are paper, wood, Straw, leather, skins or natural fiber materials like Cotton, wool, silk, jute, sisal, hemp, flax and their transformation products such as As the viscose fiber, nitrate silk or copper rayon (rayon). Application of the dyes according to claims 1-17 or their oxidation products as wheat dyes, for. For coloring of natural substances. Examples are paper, wood, straw, leather, skins or natural fiber materials such as cotton, wool, Silk, jute, sisal, hemp, flax and their transformation products such as z. As the viscose fiber, nitrate silk or copper rayon (rayon). preferred Salts for pickling are aluminum, chromium and iron salts. Application of the dyes according to claims 1-17 or their oxidation products as colorants, for. For coloring paints, varnishes and other paints, paper inks, printing inks, Inks and other colors for painting, writing and coloring purposes all kinds. Application of the dyes according to claims 1-17 or their oxidation products as pigments in electrophotography: z. B. for dry copying systems (Xerox process) and laser printers ( "Non-Impact Printing"). Application of the dyes according to claims 1-17 or their oxidation products for security marking purposes, being the great chemical and photochemical resistance and possibly also the fluorescence of the substances is of importance. This is preferred for checks, check cards, banknotes Coupons, documents, identity documents and the like, in which a special, unmistakable color impression is to be achieved. Application of the dyes of claim 1-17 or their oxidation products as an additive to other colors, at which a certain color shade is to be achieved, are preferred particularly bright shades. Application of the dyes of claim 1-17 or their oxidation products for marking objects for machine recognition of these objects the fluorescence, preferred is the machine detection of objects to sort, z. B. also for the recycling of plastics. Application of the dyes of claim 1-17 or their oxidation products as fluorescent dyes for machine-readable markings, preferably alphanumeric imprints or Barcodes. Application of the dyes according to claims 1-17 or their oxidation products for the frequency conversion of light, for. B. from short-wave light longer-wave, visible To make light. Application of the dyes of claim 1-17 or their oxidation products in display elements for many Display, hint and marking purposes, e.g. Passive display elements, information and traffic signs, such as traffic lights. Use of the dyes according to claim 1-17 or their oxidation products in ink jet in homogeneous solution as an ink or as a fluorescent ink. Application of the dyes according to claims 1-17 or their oxidation products as starting material for superconducting organic materials. Application of the dyes according to claims 1-17 or their oxidation products for solid fluorescence labels. Application of the dyes of claim 1-17 or their oxidation products for decorative purposes. Application of the dyes according to claims 1-17 or their oxidation products for artistic Purposes. Application of the dyes according to claims 1-17 or their oxidation products for tracer purposes, eg. In biochemistry, Medicine, technology and science. Here you can the dyes are covalently linked to substrates or via Nebenvalenzen such as hydrogen bonds or hydrophobic Interactions (adsorption). Application of the dyes according to claims 1-17 or their oxidation products as fluorescent dyes in highly sensitive Detection methods. Application of the dyes according to claims 1-17 or their oxidation products as fluorescent dyes in scintillators. Application of the dyes according to claims 1-17 or their oxidation products as dyes or fluorescent dyes in optical light collection systems. Application of the dyes according to claims 1-17 or their oxidation products as dyes or fluorescent dyes in fluorescence solar collectors. Application of the dyes according to claims 1-17 or their oxidation products as dyes or fluorescent dyes in fluorescence-activated displays. Application of the dyes according to claims 1-17 or their oxidation products as dyes or fluorescent dyes in cold light sources for light-induced polymerization for illustration of plastics. Application of the dyes according to claims 1-17 or their oxidation products as dyes or fluorescent dyes for material testing, z. B. in the manufacture of semiconductor circuits. Application of the dyes according to claims 1-17 or their oxidation products as dyes or fluorescent dyes for the investigation of microstructures of integrated semiconductor devices. Application of the dyes according to claims 1-17 or their oxidation products as dyes or fluorescent dyes in photoconductors. Application of the dyes according to claims 1-17 or their oxidation products as dyes or fluorescent dyes in photographic processes. Application of the dyes according to claims 1-17 or their oxidation products as dyes or fluorescent dyes in display, lighting or image converter systems in which the Excitation by electrons, ions or UV radiation takes place, for. B. in fluorescent displays, Braun tubes or in fluorescent tubes. Application of the dyes according to claims 1-17 or their oxidation products as dyes or fluorescent dyes as part of a semiconductor integrated circuit, the dyes as such or in conjunction with other semiconductors z. B. in shape an epitaxy. Application of the dyes according to claims 1-17 or their oxidation products as dyes or fluorescent dyes in chemiluminescent systems, e.g. B. in chemiluminescent light rods, in Luminescence immunoassays or other luminescence detection method. Application of the dyes according to claims 1-17 or their oxidation products as dyes or fluorescent dyes as signal colors, preferably for the visual highlighting of logotypes and Drawings or other graphic products, to mark of signs and other objects, where a special one optical color impression is to be achieved. Application of the dyes according to claims 1-17 or their oxidation products as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for production of laser beams. Application of the dyes according to claims 1-17 or their oxidation products as dyes in dye lasers as a Q-switch switch. Application of the dyes according to claim 1-17 or their oxidation products as active substances for nonlinear optics, z. B. for the Fre frequency doubling and the frequency tripling of laser light. Use of the dyes according to claims 1-175 or their oxidation products for leak testing closed Systems. Application of the dyes according to claims 1-17 or their oxidation products as Rheologieverbesserer. Application of the dyes according to claims 1-17 for calibrating spectrometers, preferably ESR spectrometer (electron spin resonance). Application of the dyes according to claims 1-17 as NIR dyes. Application of the dyes according to claims 1-17 as thermal protection dyes. Application of the dyes according to claims 1-17 as light-absorbing substances in thermal solar collectors. Application of the dyes according to claims 1-17 in the plastic layer of laminated glass, preferably as protection against NIR radiation and this preferably in the automotive industry. Application of the dyes according to claims 1-17 to promote water evaporation in salines, preferred embedded in plastic parts and preferably embedded here in plastic balls, and here the preferred ones mentioned under 24 Plastic materials.