DE102007063051A1 - New perylene bisimide compounds useful as pigments for glue-, aquarel- and water- colors, for mass coloring of polymers, preferably e.g. polyvinyl chloride, polyacrylic acid and/or their copolymers and in display elements of sign boards - Google Patents

Abstract

Perylene bisimide compounds (Q) are new. Perylene bisimide compounds (Q) of formula (I) or (II) are new. R 5>-R 5>H or 37C-alkyl residue, where 1-10 CH 2-units are optionally substituted by carbonyl groups, O, S, Se, Te, cis or trans-CH=CH-groups, where one CH unit is optionally substituted by N, C?=C, 1,2-, 1,3 - or 1,4-substituted phenyl residues, 2,3, 2,4, 2,5, 2,6, 3,4 - or 3,5-disubstituted pyridine residues, 2,3, 2,4, 2,5 or 3,4-disubstituted thiophene residues, 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 2,3, 2,6 or 2,7-disubstituted naphthalene residues, where one or two groups of CH are optionally substituted by N, 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 1,9, 1,10, 2,3, 2,6, 2,7, 2,9, 2,10- or 9,10-disubstituted anthracene residues, where one or two CH groups are optionally substituted by N, up to 12 H atoms of CH 2-groups are optionally substituted on the same carbon atoms by halogens, CN or up to 18C-alkyl, where 1-6 CH 2-units are optionally substituted by carbonyl, O, S, Se, Te, cis or trans-CH=CH-groups, where one CH-unit is optionally substituted by N, C?=C, 1,2, 1,3 or 1,4-substituted phenyl residues, 2,3, 2,4, 2,5, 2,6, 3,4- or 3,5-disubstituted pyridine residues, 2,3, 2,4, 2,5- or 3,4-disubstituted thiophene residues, 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 2,3, 2,6- or 2,7-disubstituted naphthalene residues, where 1-2C are optionally substituted by N, 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 1,9, 1,10, 2,3, 2,6, 2,7, 2,9, 2,10- or 9,10-disubstituted anthracene residues, where 1-2C are optionally substituted by N, up to 12 H of the CH 2of the alkyl residues are optionally substituted on the same carbon atoms by halogen, CN or up to 18C-alkyl, where 1-6 CH 2-units are optionally substituted by carbonyl, O, S, Se, Te, cis or trans-CH=CH-groups, where one CH-unit is optionally substituted by N, C?=C groups, 1,2, 1,3- or 1,4-substituted phenyl residues, 2,3, 2,4, 2, 5, 2,6, 3,4- or 3,5-disubstituted pyridine residues, 2,3, 2,4, 2,5- or 3,4-disubstituted thiophene residues, 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8-2,3, 2,6- or 2,7-disubstituted naphthalene residues, where 1-2C are optionally substituted by N, 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 1,9, 1,10, 2,3, 2,6, 2,7, 2,9, 2,10- or 9,10-disubstituted anthracene residues, where 1-2C are optionally substituted by N, up to 12 single hydrogen atoms of the CH 2groups are replaced by F, Cl, Br or I, CN or up to 18C-alkyl, in which 1-6 CH 2units are replaced by carbonyl, O, S, Se, Te, cis or trans -CH = CH-groups, with which one CH unit is optionally replaced also by N, C?=C-groups, 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 replaced 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 with which one or two carbon atoms are N, where up to 12 single H of CH 2-group of the alkyl is substituted by F, Cl, Br or I or CN or linear up to 18C-alkyl, with which 1-6 CH 2-units are replaced by carbonyl, O, S, Se, Te, cis or trans-CH=CH-groups, with which a CH unit optionally substituted by N, acetylenic C?=C-groups 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 C atoms are replaced 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 C are replaced by N; and X : a spacer group. Provided that: instead of the substituents, the free valences of the methyne groups and/or the quaternary carbon-atoms are linked in pairs, to form a ring, e.g. cyclohexane ring, and the R 1>-R 5>residues further contain F, Cl, Br or I. [Image].

Description

State of the art

fluorescent labels get an increasing importance. The uncomplicated and sensitive Detectability of fluorescent compounds make this species the marking particularly attractive. The fluorescence of diluted Solutions strictly follows a linear relationship with the Concentration of the analyte, so that detects the smallest concentrations can be. The method looks and falls, however with the properties of the fluorescent structures that coincide with the respective substrate are linked.

Here the perylenetetracarboxylic bisimides 1 are particularly interesting, because they not only fluoresce with quantum yields close to 100% and are unusually lightfast, giving them very high intensity Light sources can be excited optically, but about it also chemically extremely resistant They are compatible with almost all substrates are. There have been various attempts to use the perylene dyes 1 [1,2] for fluorescence labeling. Very different Methods for marking have been developed that each individually matched to the substrates. A universal one Linking with substrates with a variety of functional groups is tolerable break one significant progress.

task

The The object of the invention was the development of a universal fluorescent marker, which is compatible with a variety of functional groups is.

description

With the 1,3-dipolar cycloaddition, [3] a universal method for the construction of heterocycles is available. In the majority of these reactions, the reacting components are compatible with the majority of the functional groups, so that they also represent a universal method for building carbon skeletons. In the specific case of the reaction of azide-terminated azides, the reaction can be catalytically accelerated by the use of copper (I) compounds so that it proceeds rapidly at room temperature; This cycloaddition is known as the "click reaction" [4,5,6,7] and because of its mild reaction conditions as well as its compatibility with many functional groups, it is very well suited for linking to biologically active substrates We have used as fluorophore Perylenetetracarbonsäurebisimide, which are known for their chemical, thermal and photochemical stability and have their inherent poor solubility by introducing the long-chain sec-alkyl radical 1-hexylheptyl ("dovetail radical ") overcome. The other nitrogen atom was provided with a structure capable of linking. As shown in Scheme 1, we have incorporated a terminal alkyne to link to substrates containing azide groups. For this purpose, the perylene-anhydride-carboxylic acid imide 2 was condensed with 4-aminophenylacetylene and thus obtained a linking reagent for azides. As a pattern reaction, we have converted benzyl azide to 4a - the labeling reactions proceeded surprisingly complete and rapidly, despite the high molecular weight of the reagent, resulting in a surprisingly strong fluorescent compound; neither the heterocyclic linker nor the substrates disturbed in some way. In an analogous reaction, we converted propargylamine into 5 and then on to the labeled compounds 6a and 6b, which fluoresce similarly strongly. This is particularly noteworthy in 6b, since obviously the strong electron-donating amino group does not bother.

The examples demonstrate the broad applicability of the labeling method. On the other hand, it is difficult for some substrates to introduce azide groups. To further extend the applications of fluorescent labeling, we investigated whether it is possible to reverse the reacting units. Condensation of perylene anhydrides to perylene carboxylic imides, however, requires relatively harsh reaction conditions, which are problematic for building blocks containing azide units. We have condensed the (4-aminomethylphenyl) methanol into the anhydride-carboxylic acid imide 2 to subsequently introduce the azide group and obtain the hydroxy derivative 7. By activation, the hydroxy group with triphenylphosphine and carbon tetrabromide has been converted into bromide 8, which has been able to achieve nucleophilic exchange with azide 9; please refer 2 , The "click" reaction to fluorescently connect with 9 to 10 was remarkably smooth with a variety of substrates containing electron-rich or electron-poor double bonds, which posed problems for phenylacetylene and 3,3-dimethylbut-1-in; Be made responsible for this.

The 1,3-dipolar click reaction is so amazing smooth, that they are also applied to complex natural products can be, as exemplified by the marking of the male Hormone Ethisteron to 10g and the female hormone drug Mestranol could be demonstrated to 10h. Such substances are not only suitable by hormone titres by competitive receptorsays To determine people, but they can also for the detection of unauthorized hormone treatments such. For example Doping purposes in sports, be used.

Experimental part

General. IR Spectra: Perkin Elmer 1420 Ratio Recording Infrared Spectrometer, FT 1000; UV / Vis spectra: Varian Cary 5000 and Bruins Omega 20; Fluorescence spectra: Perkin Elmer FS 3000 (fully corrected); NMR spectroscopy: Varian Vnmrs 600 (600 MHz); Mass spectrometry: Finnigan MAT 95.

N- [1- (4-ethynylphenyl)] - N '- (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic acid bis-imide (2): N- (1-hexylheptyl) perylene-3,4: 9,10-Tetracarboxylic acid 3,4-anhydride-9,10-imide (1, 1.50 g, 2.62 mmol) was refluxed to 100 with 4-ethynylaniline (0.378 g, 3.14 mmol) in imidazole (10.0 g) for 90 minutes C., allowed to cool, dissolved with a little ethanol, precipitated with 2N hydrochloric acid, filtered off with suction, washed with 2N hydrochloric acid, dried at 110.degree. C. in a drying oven, chromatographed (silica gel, chloroform), taken up in a little dichloromethane, precipitated with methanol, filtered off and dried at 110 ° C. Y. 543 mg (31%) dark red dye, mp> 300 ° C. R _f (silica gel, chloroform) = 0.09. IR (KBr): v ~ = 2955 (m), 2923 (m), 2855 (m), 1696 (s), 1655 (s), 1592 (s), 1576 (s), 1506 (m), 1483 ( w), 1458 (w), 1432 (m), 1403 (m), 1340 (s), 1301 (m), 1251 (s), 1196 (m), 1174 (s), 1137 (m), 1124 ( m), 1108 (m), 1020 (w), 966 (m), 890 (w), 840 (m), 808 (s), 795 (s), 744 (s), 725 cm ^-1 (m) , ¹ H-NMR (600 MHz, CDCl _3, 25 ° C): δ = 0.83 (t, ³ J _{H, H} = 7.1 Hz, 6H, CH _3), 1:21 to 1:36 (m, 16H, CH _2), 1.85 -1.91 (m, 2H, β-CH ₂ ), 2.22-2.28 (m, 2H, β-CH ₂ ), 3.16 (s, 1H, C≡CH), 5.19 (tt, ³ J _{H, H} = 5.8 Hz , 3 J _{H, H} = 9.3 Hz, 1H, α-CH), 7.33-7.70 (m, ³ J _{H, H} = 8.5 Hz, ⁴ J _{H, H} = 214.9 Hz, 4H, H _arom), 8.62-8.73 ppm (m, 8H, H _perylene ). ¹³ C-NMR (150 MHz, CDCl _3, 25 ° C): δ = 14.04, 22:58, 26.94, 29.21, 31.76, 32.37, 54.85, 78.44, 83.16, 123.14, 123.26, 123.58, 126.61, 126.90, 129.00, 129.73, 130.05, 130.06, 131.30, 132.10, 133.39, 134.42, 135.48, 135.59, 163.57 ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 459 (0.22), 490 (0.61), 527 (1.0). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 539 (1.0), 582 (0.40). Fluoreszenzquantenausb. (CHCl ₃ , λ _exc = 491 nm, E _{491 nm} = 0.0257 cm ^-1 , 1a with Φ = 1.00): 1.00. HRMS (C ₄₅ H ₄₀ N ₂ O ₄ ): Ber. m / z: 672,298; Gef. M / z: 672.297, Δ = 1 mmu. C ₄₅ H ₄₀ N ₂ O ₄ (672.8): Calcd. C 80.33, H 5.90, N 4.16; Gef. C 79.10, H 5.92, N 4.03.

N- [4- (1-Benzyl-1 H - [1,2,3] triazol-4-yl) phenyl] -N '- (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic acid bisimide ( 4a): N- (4-Ethynylphenyl) -N '- (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic bisimide (3. 100 mg, 0.149 mmol) was dissolved in 20 mL of tetrahydrofuran in equimolar amounts Benzyl azide (19.8 mg, 0.149 mmol), copper (I) iodide (28.4 mg, 0.149 mmol) and N-ethyl-di- (isopropyl) amine (19.3 mg, 0.149 mmol), stirred for two days at room temperature, the copper ( I) iodide filtered off, the solvent was removed by rotary evaporation, the residue was chromatographed (silica gel, dichloromethane / methanol 100: 1, elution of the starting material and a by-product), dissolved in a little dichloromethane, precipitated with methanol, filtered off with suction and dried at 110.degree. Y. 20.0 mg (17%) of red dye, mp> 300 ° C, R _f (silica gel, dichloromethane / methanol = 30: 1) = 0.69. IR (KBr): v ~ = 2953.5 (m), 2921.9 (m), 2853.4 (m), 1690.2 (m), 1644.8 (s), 1591.5 (s), 1576.0 (m), 1505.1 (w), 1480.9 ( w), 1455.9 (w), 1434.0 (w), 1403.5 (w), 1343.0 (m), 1249.8 (m), 1199.0 (w), 1175.9 (m), 1126.3 (w), 1107.0 (w), 1076.1 ( w), 1058.3 (w), 1024.7 (w), 980.0 (w), 964.2 (w), 863.3 (w), 843.5 (w), 810.8 (w), 796.0 (w), 746.8 (w), 727.8 (w), 696.0 cm ^-1 (w). ¹ H-NMR (600 Hz, CDCl _3, 25 ° C): δ = 0.83 (t, ³ J _{H, H} = 7.1 Hz, 6H, CH _3), 1:23 to 1:36 (m, 16H, CH _2), 1.85 -1.90 (m, 2H, β-CH ₂ ), 2.22-2.29 (m, 2H, β-CH ₂ ), 5.17-5.22 (m, 1H, α-CH), 5.73 (s, 2H, CH ₂ ), 7.33-7.47 (m, 9H, H _arom ), 8.21 (s, 1H, C = CH-N), 8.68-8.77 ppm (m, 8H, H _perylene ). ¹³ C-NMR (150 MHz, CDCl _3, 25 ° C): δ = 14.04, 22:58, 26.93, 29.21, 29.70, 31.76, 32.38, 55.05, 123.11, 123.25, 123.38, 127.80, 128.25, 128.54, 128.89, 129.00, 129.58, 129.92, 131.95, 135.28, 163.55 ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 459 (0.23), 490 (0.61), 527 (1.0). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 539 (1.0), 582 (0.40). Fluoreszenzquantenausb. _(CHCl3, λ _exc = 491 nm, E _{491 nm} = 0.0257 cm ^-1 Reference: 1a with Φ = 1.00): 1.00. HRMS (C ₅₂ H ₄₇ N ₅ O ₄ ): Ber. m / z: 805,362, Gef. m / z: 805,360. Δ = 2 mmu.

(1-Hexylheptyl) -N'-propargyl-perylene-3,4: 9,10-tetracarboxylic acid bisimide (5): N- (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic acid-3,4 Anhydride-9,10-imide (1,14 g, 1.98 mmol) is initially charged with imidazole (20 g) and heated to 90 ° C. Subsequently, propargylamine (2 ml) is added and the reaction mixture is stirred for 2 hours at this temperature. Thereafter, the reaction is stopped by adding a few milliliters of ethanol and 2N hydrochloric acid (100 mL). After cooling, the residue is filtered, washed with 2 N hydrochloric acid and dried overnight in a drying oven at 110 ° C. The next day, the crude product is taken up in chloroform and purified by chromatography (silica gel CHCl ₃ ). Yield: 780 mg (64%) of red dye, mp> 300 ° C, R _f (silica gel, chloroform) = 0.12. IR (ATR): v ~ = 3253.3 m, 2925.0 m, 2922.6 m, 2855.5 m, 1694.0 m, 1654.3 s, 1593.3 s, 1578.6 m, 1506.4 w, 1464.0 w, 1433.4 m, 1403.3 m, 1353.0 w, 1334.5 s, 1246.1 m, 1171.5 m, 1134.6 w, 1124.5 w, 1097.0 w, 984.2 w, 852.8 w, 845.2 w, 807.5 s, 746.0 m, 721.1 w, 633.9 w cm ^-1 . ¹ H-NMR (600 MHz, CDCl ₃ , 25 ° C): δ = 0.82 (t, 6H, ³ J = 7.0 Hz, CH ₃ ), 1.22- 1.36 (m, 16H, CH ₂ ), 1.84-1.90 ( m, 2H, β-CH ₂ ), 2.22-2.28 (m, 2H, β-CH ₂ ), 2.24 (s, 1H, C≡CH), 4.98 (d, 2H, ⁴ J = 2.4 Hz, CH ₂ ) , 5.10-5.28 (m, 1H, α-CH), 8.50-8.66 ppm (m, 8H, H _perylene ). ¹³ C-NMR (150 MHz, CDCl _3, 25 ° C): δ = 14.0, 22.6, 26.9, 29.2, 29.6, 31.8, 32.4, 54.9, 70.8, 78.3, 122.7, 122.9, 123.2, 126.2, 126.4, 129.4, 131.7, 135.0, 162.5 ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 459 (0.22), 490 (0.60), 526 (1.0). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 539 (1.0), 582 (0.40). Fluoreszenzquantenausb. (CHCl ₃ , λ _exc = 491 nm, E _{491 nm} = 0.0285 cm ^-1 , reference: 1a with Φ = 1.00): 1.00. HRMS (C ₄₀ H ₃₈ N ₂ O ₄ ): Ber. m / z 610,284; Gef. M / z: 610.285, Δ = 1 mmu.

N- {1 - [(4-aminophenyl) -1H- [1,2,3] triazol-4-yl] methyl} -N '- (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic acid bisimide (6b): In 125 ml of tetrahydrofuran, 500 mg of N- (1-hexylheptyl) -N '- (propargyl) perylene-3,4: 9,10-tetracarboxylic acid bisimide (5. 0.819 mmol) are dissolved. To the solution are added 4-azidoaniline hydrochloride (140 mg, 0.819 mmol), copper (I) iodide (312 mg, 1.64 mmol) and N-ethyl-di (isopropyl) amine (318 mg, 2.46 mmol). After two days of stirring at room temperature, copper (I) iodide is filtered off, and tetrahydrofuran is removed by rotary evaporation. The resulting dye is then dissolved in a little dichloromethane and applied to a silica gel filled chromatography column. The eluent used here is a mixture of dichloromethane / methanol 50: 1. After eluting the starting material, increase the polarity of the eluent. With a mixture of the composition 10: 1, the product can be eluted. The eluent is then removed by rotary evaporation, the dye dissolved in a little dichloromethane and precipitated with methanol. After the precipitate has been filtered off, it is dried at 110 ° C. Y. 289 mg (47%), mp> 300 ° C. R _f (silica gel, dichloromethane / methanol = 30: 1) = 0.43. IR (KBr): v ~ = 3368.0 w, 2952.3 (m), 2923.4 (m), 2854.6 (m), 1692.6 (s), 1650 (s), 1592.3 (s), 1576.2 (s), 1519.7 (m) , 1483.4 (m), 1460.2 (m), 1403.2 (m), 1376.7 (w), 1335.5 (s), 1299.9 (m), 1249.5 (m), 1195.0 (w), 1171.6 (m) , 1127.8 (w), 1096.2 (w), 1052.2 (w), 990.5 (w), 935.5 (w), 851.5 (w), 829.9 (m), 808.1 (s), 796.2 (w), 769.7 (w) , 752.2 (m), 740.1 (m), 671.4 (w), 692.0 (w), 671.4 (w), 635.5 (w), 612.4 (w), 588.2 cm ^-1 (w). ¹ H-NMR (600 MHz, CDCl ₃ , 25 ° C): δ = 0.83 (t, ³ J = 6.9 Hz, 6H, CH ₃ ), 1.21-1.36 (m, 16H, CH ₂ ), 1.85-1.90 ( m, 2H, β-CH ₂ ), 2.22-2.29 (m, 2H, β-CH ₂ ), 3.95 (s, 1H, NH ₂ ), 5.19 (tt, ³ J = 5.8 Hz, ³ J = 9.3 Hz, 1H, α-CH), 5:52 (s, 2H, CH ₂ -N), 6.94-7.08 (m, 4H, H _arom), 8.53-8.65 ppm (m, 8H, H _perylene). UV / Vis (CHCl _3): λ _max (E _rel) = 458 (0.22), 490 (0.60), 527 (1.0). HRMS (C ₄₆ H ₄₄ N ₆ O ₄ ): Ber. m / z 745,350; Gef. M / z 745.351, Δ = 1 mmu.

N- {1- (phenyl-1H- [1,2,3] triazol-4-yl) methyl} -N '- (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic acid bisimide (6a) In tetrahydrofuran (20 mL) are dissolved N- (1-hexylheptyl) -N '- (propargyl) perylene-3,4: 9,10-tetracarboxylic acid bisimide (5. 100 mg, 0.164 mmol). To the solution is added benzyl azide (22.0 mg, 0.164 mmol), copper (I) iodide (42.0 mg, 0.328 mmol) and N-ethyl-di (isopropyl) amine (60.0 mg, 0.328 mmol). After stirring for one day at room temperature, copper (I) iodide is filtered off and tetrahydrofuran is removed by rotary evaporation. The resulting dye is then dissolved in a little dichloromethane and applied to a silica gel filled chromatography column. The eluent used here is a mixture of dichloromethane / methanol 50: 1. After eluting the starting material, increase the polarity of the eluent. With a mixture of the composition 10: 1, the product can be eluted. The eluent is then removed by rotary evaporation, the dye dissolved in a little dichloromethane and precipitated with methanol. After the precipitate has been filtered off, it is dried at 110 ° C. Y. . 84 mg (69%) of red dye, mp> 300 ° C, R _f (silica gel, chloroform / methanol = 30: 1) = 0:12. IR (ATR): v ~ = 2952.2 m, 2922.1 m, 2854.1 m, 1687.6 m, 1642.9 s, 1592.6 s, 1577.6 m, 1505.9 w, 1456.9 w, 1433.8 m, 1402.9 m, 1341.1 s, 1248.0 m, 1216.6 w, 1166.5 m, 1125.0 w, 1050.9 w, 986.3 w, 848.9 w, 809.1 s, 793.8 w, 764.3 w, 752.4 m, 705.1 w, 623.9 w cm ^-1 . ¹ H-NMR (600 MHz, CDCl _3, 25 ° C): δ = 0.82 (t, 6H, ³ J = 7.0 Hz, CH _3), 1:22 to 1:36 (m, 16H, CH _2), 1.84-1.90 ( m, 2H, β-CH _2), 2:22 to 2:28 (m, 2H, β-CH _2), 5.18 (tt, 1H, ³ J = 5.8 Hz, ³ J = 9.4 Hz, CH-N), 5:47 (s , 2H, CH ₂ -N), 5.57 (s, 2H, CH ₂ -N), 7.31-7.36 (m, 5H, H _aryl ), 7.74 (s, 1H, H _triazole ), 8.19-8.48 ppm (m, 8H, H _perylene ). ¹³ C-NMR (600 MHz, CDCl _3, 25 ° C): δ = 14.0, 22.6, 27.0, 29.2, 31.8, 32.4, 54.4, 54.8, 122.6, 122.6, 122.9, 123.7, 125.8, 125.9, 128.3, 128.7, 129.0, 129.1, 129.2, 131.2, 134.4, 134.5, 143.4, 162.7 ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 459 (0.22), 490 (0.61), 527 (1.0). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 539 (1.0), 582 (0.40). Fluoreszenzquantenausb. (CHCl ₃ , λ _exc = 491 nm, E _{491 nm} = 0.0232 cm ^-1 , reference: 1a with 1.00): 1.00. HRMS (C ₄₇ H ₄₆ N ₅ O _4): Calcd. m / z: 744,355; Gef. M / z: 744,353, Δ = 2 mmu.

Reaction of Perylene Dye Azides:

(4-Aminomethylphenyl) methanol: LiAlH ₄ (5.8 g, 152.5 mmol) are suspended in 100 mL of THF. Subsequently, 4-cyano-benzaldehyde (5.00 g, 38.1 mmol) in THF (50 mL) is dissolved and added dropwise. After five hours of stirring under reflux, the reaction mixture is cooled and treated with 2 M NaOH. The precipitated Al (OH) ₃ is filtered off and the organic phase is washed twice with a mixture of water and dichloromethane (100 ml: 400 ml _), dried over MgSO ₄ , filtered off and freed from the solvent. The remaining colorless solid is used without further purification. Y. 1.90 g (33%) of a colorless solid, mp 79 ° C. ¹ H-NMR (200 MHz, CDCl _3, 25 ° C): δ = 3.77 (s, 2H, CH ₂ NH _2), 4.60 (s, 2H, CH ₂ OH), 7:14 to 7:31 ppm (m, 4H, H _arom ). HRMS (C ₈ H ₁₁ NO): Ber. m / z: 137,084, Gef. m / z: 137,082, Δ = 2 mmu.

N- (1-Hexylhepyl) -N '- (4-hydroxymethylbenzyl) perylene-3,4: 9,10-tetracarboxylic acid bisimide (7): N- (1-hexylheptyl) perylene-3,4: 9,10- tetracarboxylic acid 3,4-anhydride-9,10-imide (2, 1.00 g, 1.74 mmol) and imidazole (20 g) were heated to 140 ° C. under argon, with (4-aminomethylphenyl) methanol (290 mg, 2.09 mmol), stirred for 2 h at this temperature, allowed to cool, mixed with a few milliliters of ethanol, precipitated with 2 N hydrochloric acid (100 mL), allowed to stand for 1 h, filtered off, washed with 2 N hydrochloric acid, dried in a drying oven (110 ° C , 16 h), taken up in chloroform and purified by column chromatography (silica gel, chloroform / methanol = 30: 1). Y. 755 mg (62%) of red dye, mp> 300 ° C, R _f (silica gel, chloroform / methanol = 30: 1) = 0.42. IR (ATR): v ~ = 3492.0 m, 2952.5 s, 2922.7 s, 2855.2 s, 1691.3 s, 1646.8 s, 1591.9 s, 1575.6 s, 1507.9 w, 1463.9 w, 1436.1 w, 1403.3 m, 1338.6 s, 1248.2 m, 1172.2 m, 1128.6 w, 1017.8 w, 852.2 w, 823.9 w, 808.2 w, 783.8 w, 752.0 w, 724.8 w, 644.3 w, 627.9 w cm ^-1 . ¹ H-NMR (600 MHz, CDCl _3, 25 ° C): δ = 0.82 (t, 6H, ³ J = 7.0 Hz, CH _3), 1:22 to 1:36 (m, 16H, CH _2), 1.84-1.90 ( m, 2H, β-CH ₂ ), 2.22-2.28 (m, 2H, β-CH ₂ ), 4.66 (s, 2H, CH ₂ -OH), 5.18 (tt, 1H, ³ J = 5.8 Hz, ³ J = 9.4 Hz, CH-N), 5.40 (s, 2H, CH ₂ -N), 7.34 (d, 2H, ³ J = 8.2 Hz, H _aryl ), 7.58 (s, 2H, ³ J = 8.2 Hz, H _aryl ), 8.56-8.67 ppm (m, 8H, H _perylene ). ¹³ C-NMR (600 MHz, CDCl _3, 25 ° C): δ = 14.04, 22:58, 26.93, 29.21, 31.75, 32.38, 43.49, 54.82, 65.14, 122.97, 123.06, 123.20, 126.35, 126.50, 127.17, 129.33, 129.44, 129.53, 131.65, 134.29, 136.54, 140.30, 163.39 ppm. UV / Vis (CHCl _3): λ _max (ε) = 463 (82932), 492 (51242), 529 (22460). Fluorescence (CHCl _3): λ _max (I _rel) = 539 (1.00), 582 (0.40). Fluoreszenzquantenausb. (CHCl ₃ , λ _exc = 491 nm, E _{491 nm} = 0.0269 cm ^-1 , reference: 1a with 1.00): 1.00. HRMS (C ₄₅ H ₄₄ N ₂ O ₅ ): Ber. m / z: 692,324, Gef. m / z: 692,324, Δ = 0 mmu. C ₄₅ H ₄₄ N ₂ O ₅ (692.8): Ber. C 78.01, H 6.40, N 4.04; Gef. C 78.03, H 6.36, N 3.94.

N- (4-bromomethylbenzyl) -N '- (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic acid bis-imide (8): N- (1-hexylheptyl) -N' - (4-hydroxymethylbenzyl ) Perylene-3,4: 9,10-tetracarboxylic acid bis-imide (7, 500 mg, 0.72 mmol) is suspended in chloroform (50 mL). After addition of tetrabromomethane (5.00 g, 15.2 mmol) and triphenylphosphine (5.00 g, 18.8 mmol), the complete dye is dissolved. After removal of the solvent, the crude product is taken up in chloroform and purified by chromatography (silica gel, chloroform / methanol = 60: 1). Y. 485 mg (89%) of red dye, mp> 300 ° C. R _f (silica gel, chloroform / methanol 50: 1) = 0.85. IR (ATR): v ~ = 2953.1 m, 2923.1 m, 2854.7 m, 1696.0 s, 1647.7 s, 1592.3 s, 1576.1 s, 1507.6 w, 1466.3 w, 1435.7 m, 1403.6 m, 1336.2 s, 1300.2 m, 1250.3 m, 1199.1 m, 1168.6 m, 1124.5 w, 1107.2 w, 1079.5 w, 1019.3 w, 987.7 m, 848.6 m, 808.1 s, 785.5 w, 750.5 m, 740.1 m, 724.0 w, 652.0 w, 628.3 w, 615.9 w cm ^-1 , ¹ H-NMR (600 MHz, CDCl ₃ , 25 ° C): δ = 0.83 (t, 6H, ³ J = 7.0 Hz, CH ₃ ), 1.21-1.38 (m, 16H, CH ₂ ), 1.85-1.91 ( m, 2H, β-CH ₂ ), 2.22-2.28 (m, 2H, β-CH ₂ ), 4.46 (s, 2H, CH ₂ -Br), 5.19 (tt, 1H, ³ J = 5.8 Hz, ³ J = 9.4 Hz, CH-N), 5.38 (s, 2H, CH ₂ -N), 7.33 (d, 2H, ³ J = 8.3 Hz, H _aryl ), 7.56 (d, 2H, ³ J = 8.3 Hz, H _aryl ), 8.52 (d, 2H, ³ J = 8.1 Hz, _perylene ), 8.55 (d, 2H, ³ J = 8.1 Hz, _perylene ), 8.61 (d, 2H, ³ J = 8.1 Hz, H _perylene ) , 8.63-8.66 ppm (m, 2H, H _perylene ). ¹³ C-NMR (600 MHz, CDCl _3, 25 ° C): δ = 14.04, 22:58, 26.94, 29.21, 31.75, 32.38, 33.17, 43.33, 54.84, 122.92, 122.95, 123.18, 126.29, 126.42, 129.21, 129.37, 129.49, 129.61 131.59, 134.18, 134.87, 137.16, 137.33, 163.30 ppm. UV / Vis (CHCl _3): λ _max (ε) = 463 (86500), 492 (52000), 529 (19200). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 539 (1.00), 582 (0.40). Fluoreszenzquantenausb. (CHCl ₃ , λ _exc = 491 nm, E _{491 nm} = 0.0269 cm ^-1 , reference: 1a with 1.00): 1.00. HRMS (C ₄₅ H ₄₃ BrN ₂ O ₄ ): Ber. m / z: 755,242, Gef. m / z: 755,242, Δ = 0 mmu. C ₄₅ H ₄₃ BrN ₂ O ₄ (755.2): Ber. C 71.52, H 5.73, N 3.71; Gef. C 71.34, H 5.76, N 3.65%.

N- (4-azidomethylbenzyl) -N '- (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic bisimide (9): N- (4-bromomethylbenzyl) -N' - (1-hexylheptyl) perylene-3 , 4: 9,10-Tetracarboxylic acid bisimide (8, 400 mg, 0.53 mmol) is suspended in dimethylformamide (50 mL) and sodium azide (72 mg, 1.1 mmol) is added. After 2 h at 80 ° C, the reaction mixture is cooled and precipitated with water (50 mL). After filtering off and washing with water and methanol, the dye is dried in a vacuum oven at 60 ° C for one hour. The dye is obtained without further work-up. Yield: 353 mg (93%) of red dye, mp> 300 ° C. R _f (silica gel, chloroform / methanol 50: 1) = 0.85. IR (ATR): v ~ = 2956.0 m, 2922.9 m, 2855.0 m, 2100.1 m, 1695.0 s, 1647.9 s, 1592.8 s, 1576.8 s, 1507.5 w, 1466.3 w, 1436.1 m, 1403.6 m, 1338.1 s, 1301.1 m, 1249.3 m, 1171.8 m, 1124.2 w, 1107.7 w, 984.4 m, 848.2 m, 808.1 s, 771.9 w, 743.8 m, 723.0 w, 667.7 w, 628.1 w, 605.6 w cm ^-1 . ¹ H-NMR (600 MHz, CDCl ₃ , 25 ° C): δ = 0.83 (t, 6H, ³ J = 7.0 Hz, CH ₃ ), 1.21-1.38 (m, 16H, CH ₂ ), 1.85-1.91 ( m, 2H, β-CH ₂ ), 2.22-2.30 (m, 2H, β-CH ₂ ), 4.30 (s, 2H, CH ₂ -N ₃ ), 5.19 (tt, 1H, ³ J = 5.8 Hz, ³ J = 9.4 Hz, CH-N), 5.37 (s, 2H, CH ₂ -N), 7.29 (d, 2H, ³ J = 8.2 Hz, H _aryl ), 7.60 (d, 2H, ³ J = 8.0 Hz, H _aryl ), 8.42 (d, 2H, ³ J = 8.1 Hz, H _perylene ), 8.48 (d, 2H, ³ J = 8.1 Hz, H _perylene ), 8.53 (d, 2H, ³ J = 8.1 Hz, H _perylene ), 8.62 ppm (d, 2H, ³ J = 13.6 Hz, H _perylene ). ¹³ C-NMR (600 MHz, CDCl _3, 25 ° C): δ 14.04, 22:59, 26.96, 29.23, 31.76, 32.38, 43.34, 54.84, 54.85, 122.80, 123.08, 126.16, 126.26, 128.35, 129.25, 129.42, 129.68 , 131.45, 134.03, 134.69, 134.83, 137.18, 163.20 ppm. UV / Vis (CHCl _3): λ _max (ε) = 463 (84600), 492 (52000), 529 (20200). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 539 (1.00), 582 (0.40). Fluoreszenzquantenausb. (CHCl ₃ , λ _exc = 491 nm, E _{491 nm} = 0.0269 cm ^-1 , reference: 1a with 1.00): 1.00. HRMS (C ₄₅ H ₄₃ N ₅ O ₄ ): Ber. m / z: 717,327, Gef. m / z 717,327, Δ = 0 mmu. C ₄₅ H ₄₃ N ₅ O ₄ (717.9): Ber. C 75.29, H 6.04, N 9.76; Gef. C 75.06, H 6.00, N 9.27.

General test procedure for the click reaction of perylene azide with terminal alkynes:

N- (4-azidomethyl-benzyl) -N '- (1-heptyl-hexyl) perylene-tetracarboxylic acid 3,4: 9,10-bisimide (9, 100 mg, 0.139 mmol), terminal alkyne (0.556 mmol), Copper (I) iodide (132 mg, 0.695 mmol) and N-ethyl-di-iso-propylamine (72.0 mg, 0.556 mmol) are mixed in THF (15 mL) and stirred at RT overnight. Then, the CuI is filtered off and the solvent removed on a rotary evaporator. The crude product is taken up in chloroform and purified by chromatography on silica gel. With a mixture of CH ₂ Cl ₂ / MeOH 100: 1 is first starting material, then eluted with CH ₂ Cl ₂ / MeOH 15: 1, the product.

N- (1-hexylheptyl) -N'-4- (4-methoxymethyl- [1,2,3] triazol-1-ylmethyl) benzylperylene-3,4: 9,10-tetracarboxylic acid bisimide (10a): methyl propargyl ether ( 40.0 mg, 0.556 mmol) was reacted and worked up according to the general procedure. Diastereomeric excess: de (%) = 50. 68 mg (63%) of red dye, mp> 300 ° C. R _f (silica gel, chloroform / methanol 40: 1) = 0.49. IR (ATR): v ~ = 2952.3 m, 2923.2 m, 2854.2 m, 1691.1 m, 1650.4 s, 1592.6 s, 1576.9 m, 1506.7 w, 1455.8 w, 1434.9 m, 1403.0 m, 1331.6 s, 1247.8 m, 1169.1 m, 1124.8 w, w 1093.8, 1049.2 w, 1022.6 w, 982.1 w, 851.9 w, 808.6 m, 795.1 w, 743.8 m, 720.8 w, 626.2 w cm ^{-1. 1} H-NMR (600 MHz, _CDCl3, 25 ° C): major diastereomer: δ = 0.83 (t, 6H, ³ J = 7.0 Hz, CH _3), 1:21 to 1:38 (m, 16H, CH _2), 1.85-1.91 (m, 2H, β-CH ₂₎ 2.22 -2.30 (m, 2H, β-CH ₂ ), 3.33 (s, 3H, CH ₃ ), 4.50 (s, 2H, CH ₂ -O) 5.18 (tt, 1H, ³ J = 5.8 Hz, ³ J = 9.4 Hz, CH-N) 5.35 (s, 2H, CH ₂ -N), 5.48 (s, 2H, CH ₂ -N), 7.24 (d, 2H, ³ J = 8.2 Hz, H _aryl ), 7.40 (s, 1H, CH _triazole), 7:57 (d, 2H, ³ J = 8.0 Hz, H _aryl), 8.39-8.62 ppm (m, 8H, H _perylene). Minor diastereomer: δ = 0.83 (t, 6H, ³ J = 7.0 Hz, CH _3), 1:21 to 1:38 (m, 16H, CH _2), 1.85-1.91 (m, 2H, β-CH _2), 2:22 to 2:30 ( m, 2H, β-CH ₂ ), 3.34 (s, 3H, CH ₃ ), 4.46 (s, 2H, CH ₂ -O) 5.18 (tt, 1H, ³ J = 5.8 Hz, ³ J = 9.4 Hz, CH -N) 5.33 (s, 2H, CH ₂ -N), 5.54 (s, 2H, CH ₂ -N), 7.24 (d, 2H, ³ J = 8.2 Hz, H _aryl ), 7.40 (s, 1H, CH _triazole ), 7.55 (d, 2H, ³ J = 8.0 Hz, H _aryl ), 8.39-8.62 ppm (m, 8H, H _perylene ). ¹³ C-NMR (600 MHz, CDCl _3, 25 ° C): δ = 14.0, 22.6, 26.9, 29.2, 31.7, 32.4, 43.2, 53.9, 54.8, 58.3, 65.4, 65.9, 122.8, 123.1, 126.1, 126.2, 128.1, 128.4, 129.2, 129.4, 129.7, 129.9, 131.5, 133.8, 134.7, 137.8, 163.2 ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 459 (0.22), 490 (0.61), 527 (1.0). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 539 (1.0), 582 (0.40). Fluoreszenzquantenausb. (CHCl ₃ , λ _exc = 491 nm, E _{491 nm} = 0.0234 cm ^-1 , reference: 1a with 1.00): 1.00. HRMS (C ₄₉ H ₄₉ N ₅ O _5): Calcd. m / z: 787,371, Gef. m / z: 787,370, Δ = 1 mmu.

N-4- (4-acetyl- [1,2,3] triazol-1-ylmethyl) benzyl-N '- (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic acid bisimide (10e): But 3-in-2-one (38.0 mg, 0.556 mmol) was reacted and worked up according to the general procedure. Yield: 60 mg (54%) of red dye, mp> 300 ° C. R _f (silica gel, chloroform / methanol 50: 1) = 0.45. IR (ATR): v ~ = 2952.4 m, 2921.8 m, 2853.4 m, 1688.9 m, 1678.2 s, 1648.4 s, 1593.9 s, 1577.0 m, 1530.4 w, 1516.2 w, 1506.3 w, 1459.0 w, 1436.9 m, 1423.2 w, 1403.4 m, 1335.4 s, 1294.4 w, 1247.1 m, 1168.2 m, 1124.9 w, 1105.9 w, 982.9 w, 810.6 s, 744.0 m, 720.7 w, 625.8 w cm ^-1 . ¹ H-NMR (600 MHz, CDCl _3, 25 ° C): δ = 0.82 (t, 6H, ³ J = 7.0 Hz, CH _3), 1:21 to 1:38 (m, 16H, CH _2), 1.85-1.91 ( m, 2H, β-CH ₂ ), 2.22-2.30 (m, 2H, β-CH ₂ ), 2.62 (s, 3H, CH ₃ ), 5.18 (tt, 1H, ³ J = 5.8 Hz, ³ J = 9.4 Hz, CH-N) 5:38 (s, 2H, CH ₂ -N), 5:51 (s, 2H, CH ₂ -N), 7.26 (d, 2H, ³ J = 8.4 Hz, H _aryl), 7.62 (d, 2H, ³ J = 8.4 Hz, H _aryl), 7.87 (s, 1H, CH _triazole), 8.39-8.62 ppm (m, 8H, H _perylene). ¹³ C-NMR (600 MHz, CDCl _3, 25 ° C): δ = 14.0, 22.6, 26.9, 27.1, 29.2, 31.7, 32.4, 43.2, 54.2, 54.8, 122.8, 122.9, 123.2, 125.2, 126.3, 126.4, 128.6, 129.4, 129.5, 130.2, 131.7, 132.9, 134.9, 138.3, 148.3, 163.3, 192.8 ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 459 (0.23), 490 (0.61), 528 (1.0). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 539 (1.0), 582 (0.40). Fluoreszenzquantenausb. (CHCl ₃ , λ _exc = 491 nm, E _{491 nm} = 0.0246 cm ^-1 , reference: 1a at 1.00): 1.00. HRMS (C ₄₉ H ₄₇ N ₅ O _5): Calcd. m / z: 785,356, Gef. m / z: 785,356, Δ = 0 mmu.

N-4- (4-Benzyloxymethyl- [1,2,3] triazol-1-ylmethyl) benzyl-N '- (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic acid bisimide (10b): Benzyl propargyl ether (82.0 mg, 0.556 mmol) was reacted and worked up according to the general procedure. Yield: 84 mg (70%) of red dye, mp> 300 ° C. R _f (silica gel, chloroform / methanol 100: 1) = 0.43 IR (ATR): v ~ = 2952.5 m, 2922.4 m, 2853.7 m, 1691.2 m, 1651.2 s, 1592.5 s, 1576.5 m, 1514.8 w, 1506.3 w, 1453.3 w, 1434.8 m, 1402.8 m, 1333.1 s, 1301.1 w, 1248.0 m, 1217.7 w, 1170.0 m, 1124.9 w, 1105.9 w, 1047.3 w, 1022.6 w, 984.5 w, 852.0 w, 808.9 m, 742.6 m, 721.7 w, 625.9 w cm ^-1 . UV / Vis (CHCl _3): λ _max (E _rel) = 459 (0.22), 491 (0.60), 527 (1.0). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 539 (1.0), 582 (0.40). Fluoreszenzquantenausb. (CHCl ₃ , λ _exc = 491 nm, E _{491 nm} = 0.0275 cm ^-1 , reference: 1a with 1.00): 1.00. HRMS (C ₅₅ H ₅₃ N ₅ O ₅ ): Ber. m / z: 863406, Gef. m / z 863.408, Δ = 0 mmu.

N- (1-Hexylheptyl) -N'-4- (4-propyl- [1,2,3] triazol-1-ylmethyl) -benzylperylene-3,4: 9,10-tetracarboxylic acid bisimide (10f): 1 Pentyne (38.0 mg, 0.556 mmol) was reacted and worked up according to the general procedure. Diastereomeric excess: de (%) = 57. Yield: 65 mg (59%) of red dye, mp> 300 ° C., R _f (silica gel, chloroform / methanol 100: 1) = 0.10. UV / Vis (CHCl _3): λ _max (E _rel) = 459 (0.22), 490 (0.60), 527 (1.0). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 539 (1.0), 582 (0.40). Fluoreszenzquantenausb. (CHCl ₃ , λ _exc = 491 nm, E _{491 nm} = 0.0297 cm ^-1 , reference: 1a with 1.00): 1.00. IR (ATR): v ~ = 3472.9 bm, 2923.8 m, 2854.0 m, 1692.0 m, 1651.6 s, 1592.5 s, 1576.8 m, 1506.7 w, 1434.5 m, 1402.9 m, 1377.8 w, 1332.5 s, 1248.3 m, 1218.3 w, 1170.1 m, 1124.8 w, 1105.1 w, 1046.1 w, 1020.8 w, 984.8 w, 852.6 w, 808.7 s, 743.3 m, 720.8 w, 626.8 w cm ^-1 . ¹ H-NMR (600 MHz, CDCl _3, 25 ° C): major diastereomer: δ = 0.82 (t, 6H, ³ J = 7.0 Hz, CH _3), 0.90 (t, 3H, ³ J = 8.2 Hz, CH ₃ ), 1.21-1.38 (m, 16H, CH ₂ ), 1.60-1.65 (m, 2H, CH ₂ ) 1.86-1.92 (m, 2H, β-CH ₂ ), 2.22-2.30 (m, 2H, β-CH ₂ ), 2.65 (t, 2H, ³ J = 7.6 Hz, CH ₂ ), 5.18 (tt, 1H, ³ J = 5.8 Hz, ³ J = 9.4 Hz, CH-N) 5.35 (s, 2H, CH ₂ - N, 5.47 (s, 2H, CH ₂ -N), 7.23 (d, 2H, ³ J = 8.2 Hz, _aryl ), 7.22 (s, 1H, CH _triazole ), 7.57 (d, 2H, ³ J = 8.2 Hz, H _aryl ), 8.37-8.60 ppm (m, 8H, H _perylene ). Sub-diastereomer: δ = 0.82 (t, 6H, ³ J = 7.0 Hz, CH ₃ ), 0.91 (t, 3H, ³ J = 8.2 Hz, CH ₃ ), 1.21-1.38 (m, 16H, CH ₂ ), 1.65- 1.70 (m, 2H, CH ₂ ), 1.86-1.92 (m, 2H, β-CH ₂ ), 2.22-2.30 (m, 2H, β-CH ₂ ), 2.58 (t, 2H, ³ J = 7.6 Hz, CH ₂ ), 5.18 (tt, 1H, ³ J = 5.8 Hz, ³ J = 9.4 Hz, CH-N) 5.33 (s, 2H, CH ₂ -N), 5.51 (s, 2H, CH ₂ -N), 7.23 (d, 2H, ³ J = 8.2 Hz, H _aryl), 7.24 (s, 1H, CH _triazole), 7:54 (d, 2H, ³ J = 8.0 Hz, H _aryl), 8.37-8.60 ppm (m, 8H , _Perylene ). ¹³ C-NMR (600 MHz, CDCl _3, 25 ° C): δ = 13.7, 14.0, 22.5, 22.6, 27.0, 27.3, 29.2, 31.7, 32.3, 43.3, 54.1, 54.9, 121.0, 122.7, 122.8, 122.8, 123.1, 126.1, 126.2, 127.9, 128.3, 129.2, 129.4, 129.6, 129.8, 131.4, 133.8, 133.9, 134.7, 137.8, 163.2 ppm. HRMS (C ₅₀ H ₅₁ N ₅ O ₄ ): Ber. m / z: 785,394, Gef. m / z: 785,394, Δ = 0 mmu.

N-4- {4 - [(benzylmethylamino) methyl] - [1,2,3] triazol-1-ylmethyl} benzyl-N '- (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic acid bisimide (10d): N-Benzyl-N-methylpropargylamine (89.0 mg, 0.556 mmol) was reacted and worked up according to the general procedure. Yield: 89 mg (93%) of red dye, mp> 300 ° C. R _f (silica gel, chloroform / methanol 70: 1) = 0.20. IR (ATR): v ~ = 3486.8 bm, 2923.9 m, 2853.9 m, 1692.1 m, 1651.8 s, 1592.5 s, 1576.7 m, 1506.7 w, 1434.6 m, 1402.8 m, 1377.6 w, 1332.3 s, 1248.4 m, 1217.9 w, 1170.1 m, 1124.9 w, 1105.2 w, 1045.7 w, 1021.1 w, 984.8 w, 852.9 w, 808.7 s, 743.6 m, 720.5 w, 626.5 w cm ^-1 . ¹ H-NMR (600 MHz, CDCl ₃ , 25 ° C): δ = 0.82 (t, 6H, ³ J = 7.0 Hz, CH ₃ ), 1.21-1.38 (m, 16H, CH ₂ ), 1.60-1.65 ( m, 2H, CH ₂ ) 1.86-1.92 (m, 2H, β-CH ₂ ), 2.22-2.30 (m, 2H, β-CH ₂ ), 2.28 (s, 3H, N-CH ₃ ), 2.68 (s , 2H, _N-CH2), 2.81 (s, 2H, _N-CH2), 5.18 (tt, 1H, ³ J = 5.8 Hz, ³ J = 9.4 Hz, CH-N) 5:37 (s, 2H, CH ₂ -N), 5:48 (s, 2H, CH ₂ -N), 7.24 (d, 2H, ³ J = 8.4 Hz, H _aryl), 7:34 (s, 1H, CH _triazole), 7.28-7-37 (m , 5H, H _aryl ), 7.58 (d, 2H, ³ J = 8.4 Hz, H _aryl ), 8.46-8.65 ppm (m, 8H, H _perylene ). ¹³ C-NMR (600 MHz, CDCl _3, 25 ° C): δ = 14.0, 22.6, 26.9, 29.2, 31.7, 32.4, 43.3 53.9, 54.8, 122.8, 122.9, 123.2, 126.2, 126.4, 128.3, 128.5, 129.4 , 129.5, 129.9, 131.6, 133.9, 134.8, 137.7, 163.3 ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 459 (0.22), 491 (0.60), 527 (1.0). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 539 (1.0), 582 (0.40). Fluoreszenzquantenausb. (CHCl ₃ , λ _exc = 491 nm, E _{491 nm} = 0.0303 cm ^-1 , reference: 1a with 1.00): 1.00. HRMS (C ₅₆ H ₅₅ N ₆ O ₄ ): Ber. m / z: 877.441, Gef. m / z: 877.439, Δ = 2.2 mmu.

N-4- (4-Dimethylaminomethyl- [1,2,3] triazol-1-ylmethyl) benzyl-N '- (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic acid bis-imide (10c): N Dimethyl propargylamine (46.0 mg, 0.556 mmol) was reacted and worked up according to the general procedure. Diastereomeric excess: de (%) = 81. 83 mg (75%) of red dye, mp> 300 ° C. R _f (silica gel, chloroform / methanol 70: 1) = 0.15. IR (ATR): v ~ = 3487.0 bm, 2922.0 m, 2853.8 m, 1692.2 m, 1655.8 s, 1592.9 s, 1576.8 m, 1499.4 w, 1455.0 w, 1435.3 m, 1403.1 m, 1352.8 w, 1329.9 s, 1247.7 m, 1217.5 w, 1169.0 m, 1125.6 w, 1103.3 w, 1042.8 w, 1021.9 w, 983.3 w, 853.0 w, 808.8 s, 743.7 m, 720.5 w, 627.0 w cm ^-1 . ¹ H-NMR (600 MHz, CDCl ₃ , 25 ° C): main diastereomer: δ = 0.82 (t, 6H, ³ J = 7.0 Hz, CH ₃ ), 1.21-1.38 (m, 16H, CH ₂ ), 1.86- 1.92 (m, 2H, β-CH ₂ ), 2.22-2.30 (m, 2H, β-CH ₂ ), 2.51 (s, 6H, CH ₃ ), 3.92 (s, 2H, N-CH ₂ ) 5.18 (tt , 1H, ³ J = 5.8 Hz, ³ J = 9.4 Hz, CH-N) 5:38 (s, 2H, CH ₂ -N), 5:49 (s, 2H, CH ₂ -N), 7.24 (d, 2H, ³ J = 8.3 Hz, H _aryl), 7:58 (d, 2H, ³ J = 8.3 Hz, H _aryl), 7.86 (s, 1H, CH _triazole), 8.55-8.67 ppm (m, 8H, H _perylene). Minor diastereomer: δ = 0.82 (t, 6H, ³ J = 7.0 Hz, CH _3), 1:21 to 1:38 (m, 16H, CH _2), 1.86-1.92 (m, 2H, β-CH _2), 2.22-2.30 (m, 2H, β-CH ₂ ), 2.51 (s, 6H, CH ₃ ), 3.92 (s, 2H, N-CH ₂ ) 5.18 (tt, 1H, ³ J = 5.8 Hz, ³ J = 9.4 Hz, CH-N) 5.40 (s, 2H, CH ₂ -N), 5.54 (s, 2H, CH ₂ -N), 7.24 (d, 2H, ³ J = 8.3 Hz, H _aryl ), 7.63 (i.e. , 2H, ³ J = 8.3 Hz, H _aryl), 7.86 (s, 1H, CH _triazole), 8.55-8.67 ppm (m, 8H, H _perylene). ¹³ C-NMR (600 MHz, CDCl _3, 25 ° C): δ = 14.0, 22.6, 26.9, 29.2, 31.7, 32.4, 43.3, 43.5, 53.2, 54.0, 54.8, 122.9, 123.0, 123.2, 126.3, 126.5, 128.3, 128.7, 129.4, 129.5, 129.9, 130.2, 131.7, 133.6, 134.2, 134.9, 137.9, 163.4 ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 459 (0.22), 489 (0:59), 528 (1.0). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 539 (1.0), 582 (0.40). Fluoreszenzquantenausb. (CHCl ₃ , λ _exc = 491 nm, E _{491 nm} = 0.0314 cm ^-1 , reference: S13 with 1.00): 1.00. MS (DEI ⁺ / 70 eV): m / z (%) = 801.9 (1) [M ⁺ + H], 800.9 (2) [M ^+], 757.8 (15) 676.6 (77) 675.6 (77) , 495.2 (65), 494.1 (100), 390.1 (55), 374.1 (12), 346.1 (36), 182.2 (12).

N- (1-hexylheptyl) -N'-4- [4- (17-hydroxy-3-methoxy-13-methyl-7,8,9,11,12,13,14,15,16,17-decahydro -6H-cyclopenta [a] phenanthren-17-yl) - [1,2,3] triazol-1-ylmethyl] benzylperylene-3,4: 9,10-tetracarboxylic bisimide (10h): mestranol (174 mg, 0.556 mmol) were reacted and worked up according to the general procedure. Y. 120 mg (84%) of red dye, mp> 300 ° C. R _f (silica gel, dichloromethane / methanol 15: 1) = 0.26. IR (ATR): v ~ = 3487.0 bm, 2924.4 m, 2853.5 m, 1693.3 m, 1654.4 s, 1592.8 s, 1576.7 m, 1498.8 w, 1434.5 m, 1403.0 m, 1377.6 w, 1332.8 s, 1249.5 m, 1169.5 m, 1124.8 w, 1104.4 w, 1041.8 w, 1020.8 w, 984.8 w, 852.2 w, 808.5 s, 743.5 m, 720.6 w, 627.8 w cm ^-1 . ¹ H-NMR (600 MHz, CDCl ₃ , 25 ° C): δ = 0.82 (t, 6H, ³ J = 7.0 Hz, CH ₃ ), 0.96 (s, 3H, CH ₃ ), 1.19-1.67 (m, 25H, CH ₂ , CH), 1.81-1.91 (m, 4H, β-CH ₂ , CH ₂ ), 2.00-2.10 (m, 2H, CH), 2.22-2.32 (m, 2H, β-CH ₂ ), 2.96-2.82 (m, 2H, CH ₂ ), 3.72 (s, 3H, OCH ₃ ), 5.15-5.20 (m, 1H, CH-N), 5.35 (s, 2H, CH ₂ -N), 5.49 (s , 2H, CH ₂ -N), 6.53 (d, 1H, ³ J = 2.7 Hz, H _aryl ), 6.60 (dd, 1H, ³ J = 2.7 Hz, 8.6 Hz, H _aryl ), 7.03 (d, 1H, ³ J = 8.6 Hz, H _aryl ), 7.25 (d, 2H, ³ J = 8.3 Hz, H _aryl ), 7.33 (s, 1H, H _triazole ), 7.58 (d, 2H, ³ J = 8.3 Hz, H _aryl ), 8.40 (d, 2H, ³ J = 8.1 Hz, _perylene ), 8.47 (d, 2H, ³ J = 8.1 Hz, _perylene ), 8.50 (d, 2H, ³ J = 8.1 Hz, H _perylene ), 8.55-8-60 ppm (m, 2H, H _perylene). ¹³ C-NMR (600 MHz, CDCl _3, 25 ° C): δ = 14.0, 14.1, 22.6, 23.3, 26.2, 26.9, 27.2, 29.2, 29.7, 31.7, 32.6, 32.9, 37.8, 39.4, 43.2, 43.3, 47.2, 48.4, 50.8, 53.8, 54.8, 55.1, 82.3, 111.3, 113.6, 121.1, 122.7, 122.8, 123.1, 126.1, 126.1, 126.3, 128.2, 129.2, 129.4, 129.8, 131.5, 132.6, 134.0, 134.1, 134.8, 137.7, 137.9, 154.1, 157.3, 163.3 ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 459 (0.22), 490 (0.60), 528 (1.0). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 539 (1.0), 582 (0.40). Fluoreszenzquantenausb. (CHCl ₃ , λ _exc 491 nm, E _{491 nm} = 0.0251 cm ^-1 , reference: 1a with 1.00): 1.00. HRMS (C ₆₆ H ₆₉ N ₅ O ₆ ): Ber. m / z: 1027,522; Gef. M / z 1027.524, Δ = 2 mmu

• [1] H. Langhals, Helv. Chim. Acta. 2005, 88, 1309–1343 .
• [2] H. Langhals, Heterocycles 1995, 40, 477–500 .
• [3] R. Huisgen, The Adventure Playground of Mechanisms and Novel Reactions in J. I Seeman (Ser. Ed.) Profiles, Pathways and Dreams. Autobiographies of Eminent Chemists, American Chemical Society, Washington DC, 1994, ISSN 1047-8329, ISBN 0-8412-1832-3 .
• [4] J. E. Moses, A. D. Moorhouse, Chem. Soc. Revs. 2007, 36, 1249–1262 .
• [5] P. Ball, Chemistry World 2007, 4, 46–48, 50–51; Chem. Abstr. 2007, 146, 461595 .
• [6] J. F. Lutz, Angew. Chem., Int. Ed. Engl. 2007, 46, 1018–1025 .
• [7] O. S. Wolfbeis, Angew. Chem. Int. Ed. Engl. 2007, 46, 2980–2982 .

N- (1-hexylheptyl) -N'-4- [4- (17-hydroxy-10,13-dimethyl-3-oxo-2,3,6,7,8,9,10,11,12,13 , 14,15,16,17-tetradecahydro-1H-cyclopenta [a] phenanthrene-17-yl) - [1,2,3] triazol-1-ylmethyl] benzylperylen-3,4: 9,10-tetracarboxylic acid bisimide (10g): Ethisterone (175 mg, 0.556 mmol) was reacted and worked up according to the general procedure. Yield: 100 mg (70%) of red dye, mp> 300 ° C. R _f (silica gel, chloroform / methanol 50: 1) = 0.10. IR (ATR): v ~ = 3476.2 bm, 2924.9 m, 2854.4 m, 1692.2 m, 1653.5 s, 1614.1 w, 1592.9 s, 1576.9 m, 1507.0 w, 1434.8 m, 1403.0 m, 1377.6 w, 1332.2 s, 1270.4 w, 1248.6 m, 1170.1 m, 1125.6 w, 1105.2 w, 1045.5 w, 1021.5 w, 985.5 w, 853.5 w, 808.9 s, 743.9 m, 720.3 w, 627.3 w cm ^-1 . ¹ H-NMR (600 MHz, CDCl _3, 25 ° C): δ = 0:30 to 0:42 (m, 1H, CH), 0.65-0.76 (m, 1H, CH), 0.83 (t, 6H, ³ J = 7.0 Hz, CH _3), 1.00 (s, 3H, CH _3), 1.15 (s, 3H, CH _3), 1:19 to 1:37 (m, 20H, CH _2), 1:42 to 1:48 (m, 2H, CH _2), 1.55-1.63 (m, 2H, CH _2), 1.77-1.96 (m, 6H, CH _2, β- CH _2), 2:02 to 2:09 (m, 1H, CH), 2:21 to 2:42 (m, 6H, ₂ CH , β-CH ₂ ), 5.15-5.20 (m, 1H, CH-N), 5.34 (s, 2H, CH ₂ -N), 5.44-5.57 (m, 2H, CH ₂ -N), 5.67 (s, 1H, H _olef ), 7.23-7.27 (m, 2H, H _aryl ), 7.35 (s, 1H, H _triazole ), 7.60 (d, 2H, ³ J = 6.9 Hz, H _aryl ), 8.41-8.63 ppm (m , 8H, H _perylene ). ¹³ C-NMR (600 MHz, CDCl _3, 25 ° C): δ = 14.0, 14.2, 17.4, 20.5, 22.6, 23.6, 27.0, 29.2, 31.5, 31.7, 32.4, 32.7, 33.9, 35.6, 36.2, 37.8, 38.5, 43.3, 47.0, 49.1, 53.1, 54.8, 122.7, 122.9, 123.2, 123.8, 126.1, 126.2, 128.3, 129.2, 129.4, 129.8, 131.5, 133.4, 134.8, 138.0, 153.5, 163.2, 171.1, 199.4 ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 459 (0.22), 490 (0.60), 527 (1.0). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 539 (1.0), 582 (0.40). Fluoreszenzquantenausb. (CHCl ₃ , λ _exc = 491 nm, E _{491 nm} = 0.0359 cm ^-1 , reference: 1a at 1.00): 1.00. HRMS (C ₆₆ H ₇₂ N ₅ O ₆ ): Ber. m / z 1030,549; Gef m / z 1030.551, Δ = 2 mmu

• [1] H. Langhals, Helv. Chim. Acta. 2005, 88, 1309-1343 ,
• [2] H. Langhals, Heterocycles 1995, 40, 477-500 ,
• [3] R. Huisgen, The Adventure Playground of Mechanisms and Novel Reactions in J. I Seeman (Ser. Ed.) Profiles, Pathways and Dreams. Autobiographies of Eminent Chemists, American Chemical Society, Washington DC, 1994, ISSN 1047-8329, ISBN 0-8412-1832-3 ,
• [4] JE Moses, AD Moorhouse, Chem. Soc. Revs. 2007, 36, 1249-1262 ,
• [5] P. Ball, Chemistry World 2007, 4, 46-48, 50-51; Chem. Abstr. 2007, 146, 461595 ,
• [6] JF Lutz, Angew. Chem., Int. Ed. Engl. 2007, 46, 1018-1025 ,
• [7] OS Wolfbeis, Angew. Chem. Int. Ed. Engl. 2007, 46, 2980-2982 ,

Subject of the invention

• 1. perylenebisimides of general formula 11,
  
  in which the radicals R ¹ to R ^{5 may 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 may 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 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 can 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 ¹⁶ may also independently of one another denote the halogen atoms F, Cl, Br or I.
• X in FIG. 11 may mean one to 12 CH ₂ units in which independently one or more may be replaced by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CH = CH groups in which one 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, 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 Anthracenreste in which one or two CH groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group or a linear alkyl chain with up to 18 C atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9, 2, 10 or 9, 10 disubs substituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which one to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit can also be replaced by a nitrogen atom, acetylenic C ≡C groups 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9-, 2,10- or r 9,10-Disubstituierte Anthracenreste in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or the quaternary carbon atoms can be linked in pairs, so that rings are formed, such. B. cyclohexane rings. The radicals R ¹ to R ⁸ can also independently of one another denote the halogen atoms F, Cl, Br or I.
• 2. perylenebisimides of general formula 12,
  
  in which the radicals R ¹ to R ⁵ and the spacer X have the meaning mentioned under 1.
• 3. Use of the substances according to 1 and 2 to fluorescence markings, preferably of natural substances. Preference is given to the 1,3-dipolar cycloaddition, most preferably a 1,3-dipolar cycloaddition using of copper (I) compounds such as copper (I) iodide.
• 4. Use of the substances according to 1 for marking azides, preferably from modified natural products. Preference is given to the 1,3-dipolar Cycloaddition, most preferably a 1,3-dipolar Xycloaddition under Use of copper (I) compounds such as copper (I) iodide.
• 5. Use of the substances according to 2 for labeling of alkynes, preferably from modified natural products. Preference is given to the 1,3-dipolar Cycloaddition, most preferably a 1,3-dipolar Xycloaddition under Use of copper (I) compounds such as copper (I) iodide.
• 6. Use of the substances according to 1 and 2 as pigments.
• Use of the substances according to 1 and 2 as pigments for glues and related colors such as 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.
• 8. Use of the substances according to 1 and 2 as pigments in paints. Preferred paints are synthetic resin paints such as acrylic or vinyl resins, Polyester lacquers, novolaks, nitrocellulose lacquers (nitro lacquers) or also natural substances such as Zaponlack, shellac or Qi-Lack (Japanlack or Chinese lacquer or East Asian lacquer).
• 9. use of the dyes according to 1 and 2 in data memories, preferably in optical memories. Examples are systems like the CD or DVD disc.
• 10. Use of the substances according to 1 and 2 as fluorescent dyes.
• 11. Use of the substances according to 1 and 2 in OLEDS (organic LEDs).
• 12. Use of the substances according to 1 and 2 in photovoltaic Attachments.
• 13. Application of the dyes of 1 and 2 for mass staining of polymers. Examples are polyvinyl chloride materials, Polyvinylidene chloride, polyacrylic acid, polyacrylamide, polyvinylbutyral, Polyvinylpyridine, cellulose acetate, nitrocellulose, polycarbonates, Polyamides, polyurethanes, polyimides, polybenzimidazoles, melamine resins, Silicones such as polydimethylsiloxane, polyesters, polyethers, polystyrene, Polydivinylbenzene, polyvinyltoluene, polyvinylbenzylchloride, polymethylmethacrylate, Polyethylene, polypropylene, polyvinyl acetate, polyacrylonitrile, polyacrolein, Polybutadiene, polychlorobutadiene or polyisoprene or the copolymers the monomers mentioned.
• 14. Application of the dyes of 1 and 2 for staining of natural substances. Examples are paper, wood, straw, or natural Fiber materials such as cotton, jute, sisal, hemp, flax or and their conversion products such. B. the viscose fiber, nitrate silk or copper rayon (Reyon).
• 15. Application of the dyes of 1 and 2 as mordant dyes, z. B. for coloring natural products. Examples are paper, Wood, straw, or natural fiber materials such as cotton, Jute, sisal, hemp, flax or their transformation products such. As the viscose fiber, nitrate silk or copper rayon (rayon). preferred Salts for pickling are aluminum, chromium and iron salts.
• 16. Application of the dyes of 1 and 2 as a colorant, z. B. for coloring paints, varnishes and other paints, Paper colors, printing inks, inks and other colors for Painting and writing purposes.
• 17. Application of the dyes of 1 and 2 as pigments in the Electrophotography: z. B. for dry copying systems (Xerox process) and laser printers (non-impact printing).
• 18. Use of the dyes of 1 and 2 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.
• 19. Application of the dyes of 1 and 2 as an additive to others Colors where a certain shade of color is to be achieved particularly bright shades are preferred.
• 20. Application of the dyes of 1 and 2 for marking articles for machine recognition of these objects the fluorescence, preferred is the machine detection of objects for Sort, z. B. also for the recycling of plastics.
• 21. Application of the dyes of 1 and 2 as fluorescent dyes for machine-readable markers, alphanumeric are preferred Imprints or barcodes.
• 22. Application of the dyes of 1 and 2 for frequency conversion from light, z. B. from short-wave light of longer wavelength, to make visible light.
• 23. Application of the dyes of 1 and 2 in display elements for many display, reference and marking purposes, z. B. passive display elements, information and traffic signs, such as Lights.
• 24. Application of Dyes of 1 and 2 in Inkjet Printers in homogeneous solution as a fluorescent ink.
• 25. Application of the dyes of 1 and 2 as starting material for superconducting organic materials.
• 26. Application of Dyes of 1 and 2 for solid fluorescence labels.
• 27. Application of the dyes of 1 and 2 for decorative Purposes.
• 28. Application of Dyes 1 and 2 for Artistic Purposes.
• 29. Use of the dyes of 1 and 2 for tracer purposes, z. B. in biochemistry, medicine, technology and science. Here, the dyes can be covalently linked to substrates or via minor valences such as hydrogen bonds or hydrophobic interactions (adsorption).
• 30. Application of the dyes of 1 and 2 as fluorescent dyes in highly sensitive detection methods.
• 31. Application of the dyes of 1 and 2 as fluorescent dyes in scintillators.
• 32. Application of the dyes of 1 and 2 as dyes or Fluorescent dyes in optical light harvesting systems.
• 33. Application of the dyes of 1 and 2 as dyes or Fluorescent dyes in fluorescence solar collectors.
• 34. Application of the dyes of 1 and 2 as dyes or Fluorescent dyes in fluorescence-activated displays.
• 35. Application of the dyes of 1 and 2 as dyes or Fluorescent dyes in cold light sources for light-induced polymerization for the representation of plastics.
• 36. Application of the dyes of 1 and 2 as dyes or Fluorescent dyes for material testing, eg. B. in the Production of semiconductor circuits.
• 37. Application of the dyes of 1 and 2 as dyes or Fluorescent dyes for the study of integrated microstructures Semiconductor devices.
• 38. Application of the dyes of 1 and 2 as dyes or Fluorescent dyes in photoconductors.
• 39. Application of the dyes of 1 and 2 as dyes or Fluorescent dyes in photographic processes.
• 40. Application of the dyes of 1 and 2 as dyes or Fluorescent dyes in display, illumination or image converter systems, where the excitation by electrons, ions or UV radiation takes place, for. B. in fluorescent displays, Braun tubes or in fluorescent tubes.
• 41. Application of the dyes of 1 and 2 as dyes or Fluorescent dyes as part of a semiconductor integrated circuit, the dyes as such or in conjunction with other semiconductors z. In the form of an epitaxy.
• 42. Application of the dyes of 1 and 2 as dyes or Fluorescent dyes in chemiluminescence systems, eg. In chemiluminescent light sticks, in luminescence immunoassays or other luminescence detection methods.
• 43. Application of the dyes of 1 and 2 as dyes or Fluorescent dyes as signal colors, preferably for optical Highlighting lettering and drawings or others graphical products, signage and others Items where a special optical color impression should be achieved.
• 44. Application of the dyes of 1 and 2 as dyes or Fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams.
• 45. Use of Dyes of 1 and 2 as Dyes in Dye Lasers as a Q-switch switch.
• 46. Application of the dyes of 1 and 2 as active substances for a nonlinear optics, e.g. B. for frequency doubling and the frequency tripling of laser light.
• 47. Application of the Dyes of 1 and 2 as Rheology Improver.
• 48. Application of dyes 1 and 2 for leak testing closed systems.

LIST OF REFERENCE NUMBERS

1 , Synthesis and Reaction of Alkyne Perylene Tetracarboxylic Bisimide Markers.

2 , Synthesis and Reaction of Alkyne Perylene Tetracarboxylic Bisimide Markers.

3 , Structures of fluorescently labeled hormones 10g and 10h.

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.

Cited non-patent literature

• - H. Langhals, Helv. Chim. Acta. 2005, 88, 1309-1343 [0025]
• H. Langhals, Heterocycles 1995, 40, 477-500 [0025]
• - R. Huisgen, The Adventure Playground of Mechanisms and Novel Reactions in J. I Seeman (Ser. Ed.) Profiles, Pathways and Dreams. Autobiographies of Eminent Chemists, American Chemical Society, Washington DC, 1994, ISSN 1047-8329, ISBN 0-8412-1832-3 [0025]
• - JE Moses, AD Moorhouse, Chem. Soc. Revs. 2007, 36, 1249-1262 [0025]
• P. Ball, Chemistry World 2007, 4, 46-48, 50-51; Chem. Abstr. 2007, 146, 461595 [0025]
• - JF Lutz, Angew. Chem., Int. Ed. Engl. 2007, 46, 1018-1025 [0025]
• - OS Wolfbeis, Angew. Chem. Int. Ed. Engl. 2007, 46, 2980-2982 [0025]

Claims (48)

Perylenebisimides of general formula 11,

in which the radicals R ¹ to R ^{5 may 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 may 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 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 can 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 ¹⁶ may also independently of one another denote the halogen atoms F, Cl, Br or I. X in FIG. 11 may mean one to 12 CH ₂ units in which independently one or more may be replaced by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CH = CH groups in which one 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 CH groups may be replaced by nitrogen atoms, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two CH groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group or a linear alkyl chain with up to 18 C atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9, 2, 10 or 9, 10 disubs substituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which one to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit can also be replaced by a nitrogen atom, acetylenic C ≡C groups 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9-, 2,10- or r 9,10-Disubstituierte Anthracenreste in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or the quaternary carbon atoms can be linked in pairs, so that rings are formed, such. B. cyclohexane rings. The radicals R ¹ to R ⁸ can also independently of one another denote the halogen atoms F, Cl, Br or I. Perylenebisimides of general formula 12,

in which the radicals R ¹ to R ⁵ and the spacer X have the meaning mentioned under 1. Use of the substances according to 1 and 2 to fluorescence markings, preferably of natural substances. Preference is given to the 1,3-dipolar cycloaddition, most preferably a 1,3-dipolar cycloaddition using of copper (I) compounds such as copper (I) iodide. Use of the substances according to 1 to mark Azides, preferably of modified natural products. Is preferred the 1,3-dipolar cycloaddition, most preferably a 1,3-dipolar one Xycloaddition using copper (I) compounds such as copper (I) iodide. Use of the substances according to 2 for labeling of alkynes, preferably of modified nature materials. Preferred is the 1,3-dipolar cycloaddition, most preferably a 1,3-dipolar cycloaddition using copper (I) compounds such as copper (I) iodide. Use of the substances according to 1 and 2 as pigments. Use of the substances according to 1 and 2 as pigments for glue colors and related colors like watercolor paints and watercolors and colors for inkjet printers, paper colors, Printing inks, inks and inks and other colors for painting and writing purposes and in paints. Use of the substances according to 1 and 2 as pigments in paints. Preferred paints are synthetic resin paints such as acrylic or Vinyl resins, polyester paints, novolaks, nitrocellulose paints (nitro paints) or natural substances such as zapon varnish, shellac or Qi varnish (Japanese varnish or Chinese lacquer or East Asian lacquer). Use of the dyes according to 1 and 2 in data memories, preferably in optical memories. Examples are systems like the CD or DVD disc. Use of the substances according to 1 and 2 as fluorescent dyes. Use of the substances according to 1 and 2 in OLEDS (organic light-emitting diodes). Use of the substances according to 1 and 2 in photovoltaic Attachments. Application of dyes 1 and 2 for mass staining of polymers. Examples are polyvinyl chloride materials, Polyvinylidene chloride, polyacrylic acid, polyacrylamide, polyvinylbutyral, Polyvinylpyridine, cellulose acetate, nitrocellulose, polycarbonates, Polyamides, polyurethanes, polyimides, polybenzimidazoles, melamine resins, Silicones such as polydimethylsiloxane, polyesters, polyethers, polystyrene, Polydivinylbenzene, polyvinyltoluene, polyvinylbenzylchloride, polymethylmethacrylate, Polyethylene, polypropylene, polyvinyl acetate, polyacrylonitrile, polyacrolein, Polybutadiene, polychlorobutadiene or polyisoprene or the copolymers the monomers mentioned. Application of the dyes of 1 and 2 for staining of natural substances. Examples are paper, wood, straw, or natural Fiber materials such as cotton, jute, sisal, hemp, flax or and their conversion products such. B. the viscose fiber, nitrate silk or copper rayon (Reyon). Application of the dyes of 1 and 2 as mordant dyes, z. B. for coloring natural products. Examples are paper, Wood, straw, or natural fiber materials such as cotton, Jute, sisal, hemp, flax or their transformation products such. As the viscose fiber, nitrate silk or copper rayon (rayon). Preferred salts For pickling are aluminum, chromium and iron salts. Application of the dyes of 1 and 2 as colorants, z. B. for coloring paints, varnishes and other paints, Paper colors, printing inks, inks and other colors for Painting and writing purposes. Application of the dyes of 1 and 2 as pigments in electrophotography: z. B. for Trockenkopiersysteme (Xerox process) and laser printers (non-impact printing). Application of the dyes of 1 and 2 for Security marking purposes, the big chemical and photochemical stability 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 should be achieved. Application of the dyes of 1 and 2 as an additive to other colors where a certain shade of color is achieved should, are particularly bright shades. Application of the dyes of 1 and 2 for marking of 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 1 and 2 as fluorescent dyes for machine-readable markers, alphanumeric are preferred Imprints or barcodes. Application of the dyes of 1 and 2 for frequency conversion from light, z. B. from short-wave light of longer wavelength, to make visible light. Application of the dyes of 1 and 2 in display elements for many display, reference and marking purposes, z. B. passive display elements, information and traffic signs, such as Lights. Application of Dyes 1 and 2 in Inkjet Printers in homogeneous solution as a fluorescent ink. Application of the dyes of 1 and 2 as starting material for superconducting organic materials. Application of the dyes of 1 and 2 for Solid fluorescent labels. Application of the dyes of 1 and 2 for decorative purposes. Application of the dyes of 1 and 2 for artistic purposes. Application of the dyes of 1 and 2 for tracer purposes, z. B. in biochemistry, medicine, technology and science. Here, the dyes can be covalently linked to substrates or via minor valences such as hydrogen bonds or hydrophobic interactions (adsorption). Application of the dyes of 1 and 2 as fluorescent dyes in highly sensitive detection methods. Application of the dyes of 1 and 2 as fluorescent dyes in scintillators. Application of the dyes of 1 and 2 as dyes or fluorescent dyes in optical light harvesting systems. Application of the dyes of 1 and 2 as dyes or fluorescent dyes in fluorescence solar collectors. Application of the dyes of 1 and 2 as dyes or fluorescent dyes in fluorescence-activated displays. Application of the dyes of 1 and 2 as dyes or fluorescent dyes in cold light sources for light-induced Polymerization for the preparation of plastics. Application of the dyes of 1 and 2 as dyes or fluorescent dyes for material testing, eg. B. at the production of semiconductor circuits. Application of the dyes of 1 and 2 as dyes or fluorescent dyes for the study of microstructures of integrated semiconductor devices. Application of the dyes of 1 and 2 as dyes or fluorescent dyes in photoconductors. Application of the dyes of 1 and 2 as dyes or fluorescent dyes in photographic processes. Application of the dyes of 1 and 2 as dyes or fluorescent dyes in display, illumination or image converter systems, where 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 of 1 and 2 as dyes or fluorescent dyes as part of a semiconductor integrated circuit, the dyes as such or in conjunction with other semiconductors z. In the form of an epitaxy. Application of the dyes of 1 and 2 as dyes or fluorescent dyes in chemiluminescent systems, e.g. In Chemiluminescent light rods, in luminescence immunoassays or other luminescence detection method. Application of the dyes of 1 and 2 as dyes or fluorescent dyes as signal colors, preferably for optical Highlighting lettering and drawings or others graphical products, signage and others Items where a special optical color impression should be achieved. Application of the dyes of 1 and 2 as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams. Application of the dyes of 1 and 2 as dyes in dye lasers as a Q-switch switch. Application of the dyes of 1 and 2 as active Substances for nonlinear optics, e.g. For example the frequency doubling and frequency tripling of laser light. Use of Dyes of 1 and 2 as Rheology Improver. Application of the dyes of 1 and 2 for leak testing closed systems.