DE102016010081A1 - An efficient synthesis for benzoperylene derivatives. Improvement of the Diels-Alder-Clar reaction - Google Patents

Abstract

Benzoperylenetetracarboxylic acid derivatives have been synthesized from perylenetetracarboxylic bisimides by reaction with maleic anhydride with the addition of chloranil as flavoring reagent. By increasing the reaction temperature, lengthening the reaction time, increasing the equivalents of chloranil and the successive addition of the chloranil, a nearly quantitative conversion could be achieved. The synthetic method was based on the reaction of imidazoloperylenebisimides. and extended by perylenedicarboximides. Perylene reacts smoothly twice to form the coronene derivative and also benzoperylenedicarboximides can be efficiently converted to the coronene derivatives. The new reaction regime has also been successfully applied to the reaction of PTAD (4-phenyltriazole-1,2,4-triazole-3,5-dione).

Description

introduction

Benzoperylene trisimides 1 [1] are gaining increasing interest as fluorescent dyes, as sensitizers [2] for singlet oxygen, [3] and as components in complex structures, [4] especially in light-harvesting systems where they can function as energy donors [5]. Because of the high photostability and comparatively high fluorescence quantum yields, the benzoperylene trisimides are of interest in such applications.

State of the art

Benzoperylene trisimides can be prepared in principle from the perylene bisimides 2 [6] via a Diels-Alder-Clar reaction [7] with maleic anhydride [8] with aromatization and subsequent condensation with primary amines. The Diels-Alder-Clar product thus represents the key substance for the representation of 1 as anhydride.

The synthetic route is efficient in terms of the number of synthetic steps and the accessibility of the starting materials, the average yields achieved by the Diels-Alder-Clar reaction are 40 to 50%, even with well-soluble perylene derivatives, but are unsatisfactory, especially because there 50% or more other material needs to be removed; This represents a considerable handicap, especially in technical syntheses. A marked increase in yield would bring considerable progress. The main reason for the low yields in the reaction can be the electron of the four carbonyl groups in the Perylenbisimiden assuming a Diels-Alder reaction as a first step, the electronic difference to the electron-poor maleic anhydride leveled; a substantial increase in yield appears hopeless under these conditions.

task

The object of the invention was to find a method which makes the benzoperylene trisimides 1 accessible from the perylene bisimides 2 in high yields.

description

We have accordingly 1 the perylene bisimide 3 which is easily soluble by its dovetail substituents (1-hexylheptyl radicals R in 1) as starting material increases the proportion of maleic anhydride in the reaction mixture to 400 to 1000 moles per mole of perylenebisimide, preferably 600 to 1000, and thus already a surprising increase in yield obtained on Benzoperylenbisimid 4 (see 1 ); the use of a large excess of maleic anhydride is because of its low price as chemical mass product unproblematic, especially since it can be easily separated and then reused. Another surprising increase in yield brought an increase in the reaction temperature from 145 ° C to 190 ° C and then further to 202 ° C (boiling point of maleic anhydride) up to 211 ° C when using boiling nitrobenzene as a solvent; This is possible because of the unusually high thermal stability of the components and the reaction product. Finally, the reaction time was extended to up to 7 days, and chloranil was added as a flavoring reagent in portions on a daily basis. These additional measures yielded an astounding increase in yield to 93.2% of isolated material, making the reaction sequence a quantitative method for the preparation of benzoperylene trisimde. The considerable increase in yield due to an increase in the reaction temperature and the amount of maleic anhydride, which had already been used in substantial excess in the originally described variant with 200 mol per mol of perylene bisimide, was at first completely unexpected, since a very large excess had already been used, however, it appears to be related to the solubility of the perylene imide starting material in the maleic anhydride melt. Of considerable advantage is the addition in portions of the chloranil, because even an additional addition of half a mole per mole of perylene bisimide leads to an increase in yield to more than 90%. The efficiency of the new reaction can be seen from the fact that to a lesser extent even a double reaction to the coronene derivative 5 ( 1 ) (MALDI: Gef. M ⁺ = 942.4, Ber. 942.4), but which was not isolated as a pure substance. An attempt to prepare the coronene derivative under the reaction conditions of the benzoperylene derivative 4, however, was not possible on a preparative scale, not even from the more electron-rich trisimide 1 (R = 1-hexylheptyl), which is also more soluble than the corresponding anhydride 4 and therefore should react more easily. Addition of nitrobenzene as solubilizer and oxidizing agent gave traces of the coronene derivative (MALDI: Gef. M ⁺ = 1122.6, Ber. 1123.6). Based on the successful implementation of perylenebisimides, we extended the synthetic process to other perylene derivatives.

The perylen bisimides 6 extended with condensed imidazole residues (see 2 ) were investigated for this purpose and, in contrast to the perylene bisimides extended with maleic acid groups, gave a surprisingly smooth conversion to 63.2% of isolated material 7, compared to 36.1% in the case of conventional reaction control; Evidently, an extension with imidazole rings, despite their electron attraction, has far less of a reactivity-reducing effect than a benzene ring carrying an anhydride function. Even the double-imidazole ring-extended system 8 (see 3 ) governed with a surprising yield of 36.1% of isolated material 9.

Furthermore, the addition product of PTAD (4-phenyltriazole-1,2,4-triazole-3,5-dione) to perylenebisimide 10 (see 4 ) reacted with maleic anhydride to give, at the position still remaining for the Diels-Alder-Clar reaction, a surprisingly smooth reaction with 71.3% yield of isolated material 11, especially considering the halved reaction time, and is also significantly higher than the corresponding one Implementation of the imidazole derivative. For this purpose, the mesomeric donor property of the nitrogen atoms linked in positions 1 and 12 in 10 is held responsible.

The efficiency of the new synthesis method is interesting for the preparation of derivatives of the systems mentioned. Here are first the unsymmetrically substituted perylene, which carry only one solubility enhancing group. Here, as in 12 for further solubility increase an extension up to 19 carbon atoms favorable (the 1-Nonydecyl radical has a considerable solubility increasing). The N-4-bromophenyl-N- (1-nonyldecyl) derivative 12 (corresponding to this concept) ( 5 ) reacts smoothly with a remarkable yield of 37.5% of isolated material 13 in this case, although a solubility-reducing effect by an aryl-bromo grouping is known. Even more surprising is the successful implementation of nitro compounds such as 14 ( 6 ), because not only do nitro groups often reduce the solubility of aromatics, but in principle they can participate with decomposition in the aromatization of the intermediate of the Diels-Alder-Clar reaction; All the more surprising is the high yield of 91.5% of isolated reaction product of N- (1-nonyldecyl) -N '- (2,3,5,6-tetramethyl-4-nitrophenyl) derivative 14 to 15, the significant proportions of Excludes decomposition. The tolerance of the reaction to nitro groups is of particular interest for the synthesis of multichromophoric compounds, as they can be reduced to primary amines and then condensed with anhydrides, such as. In Ref, [5, 9].

Carboxylic acid imide structures of the starting material were also modified. Thus, the 3,4-anhydride-9,10-dicarboximide 16 with 71.1% yield of isolated material smoothly to bisanhydride-imide 17 implement ( 7 ); this is of particular interest for synthetic applications because the five-membered and six-membered anhydrides are differentially reactive, thereby permitting the selective preparation of condensation products derived therefrom; the highly solubility-enhancing 1-nonyldecyl group is advantageous. A reaction also succeeds smoothly when a carboxylic acid imide group is removed. In the reaction of N- (1-hexylheptyl) perylene-3,4-carboxylic acid imide 18, a yield of 90.3% of reaction product 19 is achieved; please refer 8th , The use of the more solubility enhancing N-substituent 1-nonyldecyl in 20 gives a yield increase to 97.7% of 21.

The aryl carboxylic anhydride structures newly formed in such reactions can be condensed with primary amines to form bisimides, which in turn could be reacted with maleic anhydride. Here, the 1-hexylheptylamine is condensed into the simple anhydride N- (1-hexylheptyl) imide and the resulting 22 then in 23.0% yield further reacted with maleic anhydride to 23, while a condensation of 21 with 4-bromoaniline to 24 and then further led to 25 with maleic anhydride in 14.8% yield; please refer 9 ,

Another example is the benzoperylene imide 26 obtained by the condensation of 1-hexylheptylamine with the benzoperylene anhydride in question, which reacts smoothly with maleic anhydride in 32.2% to 27; please refer 10 , In the derivative 28, which is more soluble by 19 C atoms in the side chain, the yield of 29 even increases to 66.3%.

On the basis of the newly developed efficient reaction procedure, we have investigated the reaction of unsubstituted perylene (30) with maleic anhydride, which under the usual reaction conditions only leads to a simple addition, as Clar also explicitly pointed out [8]. In contrast to the mono reaction product 31, the product 32 of the double reaction can be synthesized with the reaction procedure newly developed here. Under suitable reaction conditions, the double reaction product 32 even becomes the skin product, thus offering the opportunity to synthesize coronene derivatives from perylenes in one step - a decarboxylation, such as. B. in alkaline aqueous medium at elevated temperature or with soda lime then gives unsubstituted corona. This represents a very short synthesis route for the preparation of corons. The simple and double addition product of maleic anhydride to perylene can be difficult to separate, but much easier but the corresponding carboxylic acid imides as condensation products of the crude mixture with primary amines such. B. with 1-hexylheptylamine.

The readily accessible by the new synthesis method anhydrides are as fluorescent dyes for various applications of interest, which they are characterized mainly by high fluorescence quantum yields and light fastness. The absorption spectrum of 4, for example, is hypsochromic with respect to the absorption spectrum of perylene dyes, with 3 as a typical representative - see 12 ; this effect occurs consistently in the core extension of the perylene derivatives. New is an intensive absorption band in the UV range below 400 nm, through which the dye can be used as a broadband absorber. In imidazolo derivative 9, the bathochromic color shift due to the condensed imidazoles is partially compensated by the anhydride group ring, and the absorption range of the perylene dyes is almost reached again; the absorption range of 9, even in the UV, is, however, considerably wider; please refer 13 , In the donor-substituted perylene derivative 11, a very broad light absorption is achieved covering the entire visible spectrum, and also an intense absorption at its short-wave boundary, which extends far into the UV region; please refer 14 , The unsymmetrically substituted perylene and Benzoperylenderivate 13 to 17 give very similar spectra as the corresponding symmetrically substituted compounds with partially strong fluorescence; please refer 15 to 18 , The coronene derivative 23 absorbs slightly hypsochromic compared to 3, but the strongest light absorption is in the short-wave visible and in the NIR range; please refer 19 , The carboxylic imides prepared by condensation of the anhydrides with primary amines to increase the solubility, in particular with 1-hexylheptylamine, have similar UB / Vis spectroscopic properties as the starting anhydrides, but are more stable to hydrolysis; in part, increases in the fluorescence quantum yields are observed, as can be seen in the example of FIGS. 23 and 23a. Therefore, they have advantages over the primarily obtained anhydrides for certain applications.

conclusion

Perylene derivatives, especially carboxylic acid imides, can be efficiently reacted with maleic anhydride in a Diels-Alder-Clar reaction if the reaction is carried out at elevated temperatures, such as, e.g. B. 145 ° C or higher, are carried out and as the aromatizing reagent chloranil, preferably in portions over several days, is added; An extension of the reaction time to four to seven days is also advantageous for the reaction. Perylenebisimides can thus be converted almost quantitatively to the benzoperyleneanhydride bisimides; even traces of coronene are formed in traces as Products of double reactions; otherwise these can usually not be detected in such reactions.

The new efficient Diels-Alder-Clar reaction can be based on perylene derivatives with fused-on heterocyclic rings, such as. As imidazoloperylenebisimides, be extended. Efficiently, the reaction also proceeds with perylene derivatives with fused triazolinedione rings.

Unsymmetrically substituted perylenebisimides can also be efficiently reacted under the reaction conditions. A one-sided substitution with the very strong solubility enhancing 1-nonyldecyl radical is beneficial. Finally, perylene imides with modified imide structures can be successfully implemented, such. B. anhydride imides, in which reaction products are obtained with a five-membered anhydride and a six-membered anhydride structure, which differ in further reactions in their reactivity. Perylene monoimides react to form the benzoperylene anhydride imides. Their condensation with primary amines leads to angled perylenebisimides, which can be re-reacted with maleic anhydride to form the coronene derivatives.

Unsubstituted perylene is expected to react very rapidly and under suitable reaction conditions almost completely to the coronene derivative, whereas the reaction remains at the benzoperylene derivative stage under conventional reaction conditions. Since carboxylic acids can be efficiently decarboxylated, this provides an efficient way to represent corons. Experimental part

2,10-bis (1-hexylheptyl) furo [3 ', 4': 10,11] naphtho [8 ', 1', 2 ', 3': 7,8,9] triphenyleno [2,1,12 -defg] isoquinoline-1,3,5,7,9,11 (2H, 10H) -hexaone (4) [1]: 2,9-bis (1-hexylheptyl) anthra [2,1,9-def : 6,5,10-d'e'f '] diisoquinoline-1,3,8,10 (2H, 9H) -tetraone (3, 604 mg, 0.800 mmol) and maleic anhydride (50.0 g) were stirred at 105 ° C stirred until the homogeneous melt, with chloroanil (393 mg, 1.60 mmol), stirred for 7 d at 145 ° C and after the 4th Day more chloranil (98.0 mg, 0.400 mmol) was added, after cooling in acetone (50 mL ), added to 2 M aqueous HCl (250 mL), stirred for 2 h at room temperature, aged over 16 h, filtered off with suction with a D4 glass frit, dried at 110 ° C for 16 h, purified by column chromatography (silica gel, CHCl ₃ , separation of Eduktresten, and then CHCl ₃ / HOAc 20: 1, yellow, intense green fluorescent band), after concentration with methanol like, sucked off (D4 glass frit) and 16 h at 110 ° C dried. Y. 633 mg (0.746 mmol, 93.2%) orange solid, m.p. 278 ° C. R _f (silica gel, chloroform / glacial acetic acid 20: 1) = 0.85. ¹ H-NMR (600 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.81 (t, ³ J (H, H) = 6.9 Hz, 12H, 4 x CH ₃ ), 1.18-1.45 (m, 32H , 16 × CH ₂ ), 1.90-1.99 (m, 4H, 2 × β-CH ₂ ), 2.27-2.39 (m, 4H, 2 × β-CH ₂ ), 5.24-5.35 (m, 2H, 2 × NCH ), 9.20-9.31 (m, 2H, 2 x CH _aryl ), 9.50 (d, ³ J (H, H) = 8.3Hz, 2H, 2 x CH _aryl ), 10.28-10.39 (m, 2H, 2 x CH _aryl ) ppm. MS (FAB ^- ): m / z (%): 848.7 (100) [M] ^- , 777.0 (8), 692.0 (17), 666.5 (33), 665.5 (30), 621.0 (5), 594.0 (8 ), 509.0 (6), 483.0 (9), 438.0 (6), 411.3 (11), 383.3 (8). HRMS (C ₅₄ H ₆₁ N ₂ O ₇ ): Ber. m / z: 849.4479, Gef. m / z: 849.4470; Δ = 0.0009.

Reaction product of 2,11-bis (1-hexylheptyl) -5-phenylimidazolo [4 ', 5': 3,4] anthra [2,1,9-def: 6,5,10-d'e'f '] diisoquinoline-1,10,12 (2H, 11H) -tetraon and maleic anhydride (7): 2,11-bis (1-hexylheptyl) -5-phenylimidazolo [4 ', 5': 3,4] anthra [2.1 , 9-def: 6,5,10-d'e'f '] diisoquinoline-1, -10,12 (2H, 11H) -tetraone (6,300 mg, 0.344 mmol) and maleic anhydride (50.0 g, 510 mmol ) were stirred at 100 ° C until homogeneous melt, with chloroanil (169 mg, 0.689 mmol), stirred for 7 d at 145 ° C and after the 3rd, 4th, 5th and 6th Day each further chloranil ( 42.0 mg, 0.172 mmol), after cooling still liquid in acetone (50 mL), added to 2 M aqueous HCl (250 mL), stirred for 2 h at room temperature, aged over 16 h, filtered off with suction with a D4 glass frit , washed thoroughly with 2 M aqueous HCl, dried at 110 ° C for 16 h, purified by column chromatography (silica gel, CHCl ₃ , separation of educt residues, and then CHCl ₃ / glacial acetic acid 20: 1, third, orange, intensely fluorescent band), concentrated under a rough vacuum, precipitated with distilled water, filtered off with suction (D4 glass frit) and dried at 110 ° C. for 16 h. Y. 210 mg (63.2%, 0.218 mmol) of a red solid, mp> 300 ° C. R _f (silica gel, chloroform / glacial acetic acid 20: 1) = 0.91. ¹ H NMR (600 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.78-0.89 (m, 12H, 4 x CH ₃ ), 1.17-1.80 (m, 32H, 16 x CH ₂ ), 1.97- 2.10 (m, 4H, 2 x β-CH ₂ ), 2.35-2.48 (m, 4H, 2 x β-CH ₂ ), 5.27-5.43 (m, 2H, NCH), 7.72-7.83 (m, 3H, 3 × CH _aryl ), 8.44-8.53 (m, 2H, 2 × CH _aryl ), 9.20-9.35 (m, 1H, CH _perylene ), 10.21 (s, 1H, CH _perylene ), 10.25 (s, 1H, CH _perylene ) , 11.44-11.54 (m, 1H, CH _perylene ), 11.90 (s, 1H, NH) ppm. MS (FAB ^-): m / z (%): 965.3 (100) [M + H] ^-, 964.3 (58) [M] ^-, 848.0 (20) 806.0 (31) 782.0 (50) 625.0 ( 19), 599.0 (29), 553.0 (20), 527.6 (36), 306.5 (27), 153.2 (73), 152.2 (54), 46.1 (24), 26 (17). HRMS (C ₆₁ H ₆₄ N ₄ O ₇ ): Ber. m / z: 964.4775, Gef. m / z: 964.4700; Δ = 0.0075.

Reaction product of 8,15-bis (1-hexylheptyl) phenanthra [2,1,10-def: 7,8,9-d'e'f '] - 2,5-diphenyl-1,6,10,15 tetrahydroimidizo [4,5-h: 4'5'-h] diisoquinoline-7,9,14,16-tetraone and maleic anhydride (9): 8,15-bis (1-hexylheptyl) phenanthra [2,1, 10-def: 7,8,9-d'e'f '] - 2,5-diphenyl-1,6,10,15-tetrahydroimidizo [4,5-h: 4'5'-h] diisoquinoline-7 , 9,14,16-tetrazone (8) (450 mg, 0.456 mmol) and maleic anhydride (75.0 g) were stirred at 105 ° C to homogeneous melt, with chloroanil (224 mg, 0.912 mmol), 7 d at 145 C., and after the 3rd, 4th, 5th and 6th day in each case more chloranil (56.0 mg, 0.228 mmol) was added, and after cooling, it was dispersed in liquid acetone (50 ml) to give 2M aqueous HCl ( 400 ml), stirred at room temperature for 1 h, left for 16 h, filtered off with suction with a D4 glass frit, dried at 110 ° C. for 16 h, purified by column chromatography (silica gel, CHCl ₃ , removal of educt residues, and then CHCl ₃ / Glacial acetic acid 20: 1, broad, purple, intense orange fluorescent band), concentrated in a rough vacuum, precipitated from glacial acetic acid with methanol, filtered off with suction (D4 glass frit) and dried at 110 ° C for 16 h. Y. 178 mg (36.1%, 0.165 mmol) of purple solid, mp> 300 ° C. R _f (silica gel, chloroform / glacial acetic acid 20: 1) = 0.37. IR (ATR): v ~ = 3376 (w), 3070 (vw), 2952 (m), 2922 (m), 2854 (m), 2360 (w), 2216 (vw), 2155 (vw), 1840 ( w), 1770 (m), 1702 (s), 1661 (m), 1645 (s), 1629 (s), 1567 (m), 1546 (m), 1532 (m), 1482 (m), 1457 ( s), 1420 (s), 1404 (s), 1376 (m), 1349 (m), 1313 (s), 1289 (s), 1237 (s), 1184 (vs), 1153 (s), 1116 ( s), 1068 (m), 1048 (m), 1026 (m), 978 (m), 961 (m), 934 (m), 905 (m), 870 (m), 813 (s), 776 ( s), 770 (m), 758 (s), 708 (s), 686 (vs) cm ^-1 . ¹ H-NMR (600 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.76-0.92 (m, 12H, 4 x CH ₃ ), 1.17-1.57 (m, 32H, 16 x CH ₂ ), 2.10- 2.19 (m, 4H, 2 x β-CH ₂ ), 2.40-2.58 (m, 4H, 2 x β-CH ₂ ), 5.31-5.46 (m, 2H, 2 x NCH), 7.34-8.02 (m, 6H , 6 × CH _aryl ), 8.15-8.63 (m, 4H, 4 × CH _aryl ), 10.28 (s br., 2H, 2 × CH _{benzoperylene} ), 12.44 (s br., 2H, 2 × NH) ppm. ¹³ C-NMR (150 MHz, _CDCl3, 27 ° C, TMS): δ = 13.1, 20.5, 21.6, 26.3, 28.3, 28.7, 30.4, 30.8, 31.5, 124.5, 127.7, 128.1, 128.9, 161.5 ppm. UV / Vis (CHCl ₃ ): λ _max (E _rel ) = 300.0 (1.00), 528.2 (0.95), 568.8 (0.69) nm. Fluorescence (CHCl ₃ , λ _exc = 528.0 nm): λ _max (I _rel ) = 580.9 (1.00), 628.7 (0.42) nm. Fluorescence quantum eff. (CHCl ₃ , λ _exc = 528.0 nm, E _{528.0nm / 1cm} = 0.0442, reference: 3 with Φ = 1.00): 0.24. MS (FAB ⁺ ): m / z (%): 1128.5 (6), 1114.5 (1), 1082.4 (1) [M + 2H] ⁺ , 717.7 (2), 646.8 (2).

7-phenyl-2,12-di (1-hexylheptyl) -6H-isobenzofuro [4 ', 5', 6 ', 7': 6,7] dipyrido [3 ', 4', 5 ': 3,4; 3 '', 4 '', 5 '': 9,10] peryleno [1,12-cde] [1,2,4] triazolo [1,2-a] pyridazin-1,3,6,8,11 , 13,15,17 (2H, 7H, 12H) -octaone (11): 11,12-diaza-11,12-dihydrobenzo [ghi] perylene-2,3,8,9,11,12-hexacarboxylic acid-2 , 3: 8,9-bis (1-hexyheptylimide) -11,12-phenylimide (10, 516 mg, 0.556 mmol) and maleic anhydride (40.0 g) were stirred at 105 ° C until homogeneous, with chloranil (273 mg , 1.11 mmol), stirred for 14 d at 145 ° C and after the 5th, 6th, 7th, 11th and 12th Day each additional chloranil (137 mg, 0.557 mmol) was added, after cooling still liquid in Dispersed acetone (50 mL), added to 2 M aqueous HCl (400 mL), stirred at room temperature for 16 h, filtered off with suction with a D4 glass frit, dried at 110 ° C for 16 h, purified by column chromatography (silica gel, CHCl ₃ , separation of Eduktresten , and then CHCl ₃ / methanol 5: 1, broad, blue band), concentrated in a rough vacuum, from a little glacial acetic acid with the precipitated water, filtered off with suction (D4 glass frit) and dried at 110 ° C for 16 h. Y. 405 mg (71.3%, 0.396 mmol) blue-violet solid, mp> 300 ° C. R _f (silica gel, CHCl ₃ / methanol 5: 1) = 0.53. IR (ATR): v ~ = 3130 (w), 2923 (s), 2855 (m), 1843 (m), 1775 (s), 1726 (s), 1711 (s), 1663 (s), 1620 ( w), 1598 (w), 1574 (w), 1523 (w), 1502 (w), 1488 (m), 1460 (m), 1416 (m), 1383 (s), 1346 (s), 1305 ( s), 1266 (m), 1236 (m), 1209 (w), 1196 (w), 1164 (m), 1145 (m), 1126 (m), 1034 (s), 972 (s), 925 ( m), 905 (m), 860 (w), 811 (w), 761 (s), 753 (s), 728 (m), 702 (w), 688 (m), 667 (m) cm ^-1 , ¹ H-NMR (400 MHz, CDCl _3, 25 ° C, TMS): δ = 0.76 (t, ³ J (H, H) = 6.9 Hz, 12H, 4 × CH _3), 1:09 to 1:35 (m, 32H , 16 × CH ₂ ), 1.78-1.89 (m, 4H, 2 × β-CH ₂ ), 2.14-2.27 (m, 4H, 2 × β-CH ₂ ), 5.11-5.22 (m, 2H, 2 × NCH ), 7.48 (t, ³ J (H, H) = 7.3 Hz, 1H, CH _aryl ), 7.56 (t, ³ J (H, H) = 7.6 Hz, 2H, 2 x CH _aryl ), 7.63 (d, ³ J (H, H) = 8.0 Hz, 2H, 2 x CH _aryl ), 9.73 (s, 2H, 2 x CH _perylene ), 9.93 (s, 2H, 2 x CH _perylene ) ppm. UV / Vis (CHCl ₃ ): λ _max ( _Erel ) = 325.8 (0.83), 386.6 (0.57), 408.2 (0.71), 605.6 (0.18) nm. Fluorescence (CHCl ₃ , λ _exc = 408.0 nm): λ _max ( I _rel ) = 477.3 (0.89), 509.4 (0.53), 544.1 (0.64), 730.7 (1.00) nm. Fluorescence quantum eff. (CHCl ₃ , λ _exc = 408.0 nm, E _{408.0 / 1cm} = 0.7061, reference: 3 with Φ = 1.00): 0.00 (exp. <0.01). MS (FAB ⁺ ): m / z (%): 1021.5 (26) [M + H] ⁺ , 840.4 (49), 658.2 (100), 511.2 (40), 439.2 (29), 154.2 (60), 55.1 (75). HRMS (C ₆₂ H ₆₃ N ₅ O ₉ ): Ber. m / z: 1021.4626, Gef. m / z: 1021.4627; Δ = -0.0001.

Reaction product of 2- (4-bromophenyl) -9- (1-nonyldecyl) anthra [2,1,9-def: 6,5,10-d'e'f '] diisoquinoline-1,3,8,10 ( 2H, 9H) -tetraon and maleic anhydride (13): 2- (4-bromophenyl) -9- (1-nonyldecyl) anthra [2,1,9-def: 6,5,10-d'e'f '] diisoquinoline-1,3,8,10 (2H, 9H) -tetraone (12, 323 mg, 0.398 mmol) and maleic anhydride (30.0 g, 0.306 mol) were stirred at 105 ° C until homogeneous, with chloranil (196 mg , 0.796 mmol), stirred for 7 d at 145 ° C and after the 3rd, 4th, 5th and 6th Day each additional chloroanil (49 mg, 0.199 mmol) was added, after cooling still liquid in acetone (50 mL), added to 2 M aqueous HCl (250 mL), stirred for 1 h at room temperature, allowed to age for 1 h, filtered off with suction with a D4 glass frit, dried at 110 ° C. for 16 h, purified by column chromatography (silica gel, CHCl ₃ , Separation of educt residues, and then CHCl ₃ / glacial acetic acid 20: 1, intense green fluorescent band), concentrated in a rough vacuum, precipitated from chloroform with methanol, filtered off with suction (D4 glass frit) and dried at 110 ° C. for 16 h. Y. 135 mg (37.5%, 0.149 mmol) of brown solid, mp> 300 ° C. R _f (silica gel, chloroform / glacial acetic acid 20: 1) = 0.53. IR (ATR): v ~ = 3086 (w), 2953 (w), 2921 (m), 2852 (m), 1845 (w), 1773 (m), 1706 (s), 1660 (vs), 1624 ( m), 1594 (m), 1523 (w), 1488 (m), 1456 (m), 1412 (m), 1365 (s), 1324 (s), 1294 (s), 1282 (s), 1269 ( s), 1213 (s), 1195 (s), 1169 (s), 1142 (s), 1121 (m), 1092 (m), 1071 (m), 1013 (m), 956 (m), 933 ( m), 910 (m), 833 (m), 811 (s), 792 (s), 760 (s), 745 (s), 721 (m), 689 (m), 658 (s) cm ^-1 , ¹ H-NMR (600 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.75-0.94 (m, 6H, 2 x CH ₃ ), 1.13-1.52 (m, 28H, 14 x CH ₂ ), 1.96- 2.12 (m, 2H, β-CH ₂ ), 2.27-2.48 (m, 2H, β-CH ₂ ), 5.24-5.38 (m, 1H, NCH), 7.32-7.47 (m, 2H, 2 x CH _aryl ) , 7.67-7.81 (m, 2H, 2 x CH _aryl ), 8.62-9.04 (m, 2H, 2 x CH _{benzoperylene} ), 9.04-9.59 (m, 2H, 2 x CH _{benzoperylene} ), 9.78-10.22 (m, 2H , 2 × CH _{benzoperylene} ) ppm. ¹³ C-NMR (150 MHz, _CDCl3, 27 ° C, TMS): δ = 14.1, 22.6, 27.1, 27.3, 29.3, 29.6, 31.9, 32.4, 55.7, 122.7, 122.8, 123.0, 123.3, 123.9, 124.6, 124.8, 124.9, 125.3, 126.7, 127.6, 128.1, 128.4, 128.8, 128.9, 130.4, 130.9, 131.4, 131.5, 132.7, 133.5, 133.6, 161.4, 161.5, 161.6, 162.3, 162.4, 162.8, 162.9, 167.7 ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 333.4 (0.44), 367.8 (12:32), 413.0 (12:26), 438.0 (0.65) 468.2 (1.00) nm Fluorescence (CHCl _3, λ _exc = 438.0. nm). λ _max (I _rel) = 476.8 (1.00), 511.2 (12:57), 550.0 (12:17) Fluoreszenzquantenausb nm. (CHCl ₃ , λ _exc = 438.0 nm, E _{438.0nm / 1cm} = 0.0182, reference: 3 with Φ = 1.00): 0.42. MS (DEP / EI): m / z (%): 906.0 (16) [M + 2H] ⁺ , 778.9 (2), 650.8 (3), 639.8 (100), 489.9 (13), 466.9 (25), 415.0 (10), 373.1 (2), 266.3 (12), 139.2 (6), 125.1 (17), 111.1 (37), 97.1 (72), 83.1 (87), 69.1 (97). HRMS (C ₅₃ H ₄₉ BrN ₂ O ₇ ): Ber. m / z: 904.2723, Gef. m / z: 904.2727; Δ = -0.0004. C ₅₃ H ₄₉ BrN ₂ O ₇ (905.9): Ber. C 70.27, H 5.45, N 3.09; Gef. C 69.88, H 6.23, N 2.64.

Reaction product of 2- (1-nonyldecyl) -9- (2,3,5,6-tetramethyl-4-nitrophenyl) anthra [2,1,9-def: 6,5,10-d'e'f '] diisoquinoline-1,3,8,10 (2H, 9H) -tetraone and maleic anhydride (15): 2- (1-nonyldecyl) -9- (2,3,5,6-tetramethyl-4-nitrophenyl) anthra [2 , 1,9-def: 6,5,10-d'e'f '] diisoquinoline-1,3,8,10 (2H, 9H) -tetraone (14, 0.499 g, 0.598 mmol) and maleic anhydride (50.0 g ) Was stirred at 105 ° C until the homogeneous melt, with chloroanil (289 mg, 1.18 mmol), stirred for 7 d at 145 ° C and after the 3rd, 4th, 5th and 6th day each further Chloranil (74 mg, 0.299 mmol) was added, after cooling still liquid in acetone (50 mL) dispersed, added to 2 M aqueous HCl (200 mL), stirred for 1 h at room temperature, aged over 2 h, with a D4 Glass frit filtered off, dried at 110 ° C for 16 h, purified by column chromatography (silica gel, CHCl ₃ , separation of Eduktresten, and then CHCl ₃ / glacial acetic 20: 1, second, intense green fluorescent band) and evaporated to dryness. Y. 508 mg (91.5%, 0.547 mmol) of orange solid, mp> 300 ° C. R _f (silica gel, chloroform / glacial acetic acid 20: 1) = 0.54. IR (ATR): v ~ = 3854 (w), 3745 (w), 2923 (s), 2853 (s), 2349 (w), 1844 (w), 1774 (w), 1733 (w), 1704 ( s), 1661 (s), 1625 (m), 1594 (s), 1576 (m), 1559 (w), 1529 (s), 1507 (w), 1488 (w), 1457 (m), 1435 ( w), 1412 (s), 1363 (s), 1324 (s), 1298 (s), 1264 (s), 1216 (m), 1201 (m), 1167 (s), 1138 (w), 1120 ( w), 1076 (w), 1016 (w), 968 (w), 953 (w), 932 (w), 911 (w), 846 (s), 810 (s), 762 (m), 747 ( s), 720 (w), 674 (w), 656 (w) cm ^{-1 . 1} H-NMR (600 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.80 (t, ³ J (H, H) = 7.0 Hz, 6H, 2 x CH ₃ ), 1.13-1.45 (m, 28H , 14 × CH ₂ ), 1.91-1.99 (m, 2H, β-CH ₂ ), 2.17 (s, 6H, 2 × CH ₃ ), 2.27 (s, 6H, 2 × CH ₃ ), 2.28-2.38 (m , 2H, β-CH ₂ ), 5.25-5.35 (m, 1H, NCH), 9.24-9.35 (m, 2H, 2 x CH _{benzoperylene} ), 9.56 (dd, ³ J (H, H) = 13.6 Hz, ³ J (H, H) = _8.3Hz , 2H, _{2xCH benzoperylene} ), 10.31-10.39 (m, 1H, CH _{benzoperylene} ), 10.43 (s, 1H, CH _{benzoperylene} ) ppm. ¹³ C-NMR (150 MHz, _CDCl3, 27 ° C, TMS): δ = 14.0, 15.0, 15.1, 22.6, 27.0, 29.2, 29.5, 31.8, 32.4, 55.5, 122.8, 126.1, 131.6, 133.7, 162.1 ppm , UV / Vis (CHCl _3): λ _max (E _rel) = 332.0 (0.40) 366.0 (12:13), 413.0 (12:26), 438.0 (0.65) 468.0 (1.00) nm Fluorescence (CHCl _3, λ _exc = 438.0. nm). λ _max (I _rel) = 479.0 (1.00), 513.0 (12:57), 551.0 (12:17) Fluoreszenzquantenausb nm. _(CHCl3, λ _exc = 438.0 nm, _438.0nm E _{/ 1cm} = 0.0144, reference: 3 with Φ = 1.00): 12:42. MS (FAB ^- ): m / z (%): 974.3 (23), 960.2 (21), 928.2 (100) [M + H] ⁺ , 915.2 (20), 914.2 (17), 884.1 (10), 871.1 (9), 857.1 (8), 590.7 (13), 413.5 (12), 153.2 (9), 46.1 (5).

10- (1-nonyldecyl) -1 H-furo [3 ', 4': 4,5] isochromeno [4 ', 5', 6 ': 7,8,9] pyreno [2,1,10-def] isoquinoline -1,3,5,7,9,11 (10H) -hexaone (17): 2,9-bis (1-nonyldecyl) anthra [2,1,9-def: 6,5,10-d 'e'f'] diisoquinoline-1,3,8,10-tetrazone (16, 679 mg, 1.03 mmol) and maleic anhydride (60.0 g) were stirred at 105 ° C until homogeneous, with chloranil (508 mg, 2.06 mmol ), stirred for 7 d at 145 ° C and after the 3rd, 4th, 5th and 6th Day each additional chloranil (127 mg, 0.516 mmol) was added, after cooling, still in liquid acetone (50 mL) dispersed , to 2 M aqueous HCl (300 mL), stirred for 1 h at room temperature, aged over 2 h aged, filtered with suction D4 glass frit, dried at 110 ° C for 16 h, purified by column chromatography (silica gel, CHCl ₃ , CHCl ₃ / Glacial acetic acid 50: 1, CHCl ₃ / glacial acetic acid 20: 1, second green fluorescent band, and a second chromatography of toluene / acetone / glacial acetic acid 12: 1: 0.12, separation of educt traces), dissolved in a little chloroform, precipitated with methanol lt, filtered off with suction (D4 glass frit) and dried at 110 ° C. for 16 h. Y. 552 mg (71.1%, 0.734 mmol) ocher solid, mp> 300 ° C. R _f (silica gel, chloroform / glacial acetic acid 20: 1) = 0.49. IR (ATR): v ~ = 3477 (w), 3088 (w), 2923 (s), 2853 (m), 1847 (w), 1778 (s), 1735 (s), 1705 (s), 1661 ( s), 1625 (s), 1596 (s), 1486 (w), 1456 (m), 1414 (s), 1364 (s), 1326 (s), 1312 (s), 1293 (s), 1276 ( s), 1256 (s), 1219 (s), 1174 (s), 1158 (s), 1121 (m), 1080 (m), 1017 (s), 912 (m), 846 (m), 808 ( vs), 754 (m), 743 (s), 721 (m), 672 (m), 656 (m) cm ^-1 . ¹ H-NMR (600 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.80 (t, ³ J (H, H) 6.7 Hz, 6H, 2 x CH ₃ ), 1.12-1.38 (m, 32H, 16 × CH ₂ ), 1.89-2.01 (m, 2H, β-CH ₂ ), 2.26-2.38 (m, 2H, β-CH ₂ ), 5.29 (m, 1H, α-CH ₂ ), 9.17-9.38 ( m, 2H, CH _perylene ), 9.46-9.61 (m, 2H, CH _perylene ), 10.23-10.39 (m, 2H, CH _perylene ) ppm. ¹³ C-NMR (150 MHz, _CDCl3, 27 ° C, TMS): δ = 14.0, 22.6, 27.0, 29.2, 29.5, 31.8, 32.3, 55.6 161.8 ppm. UV / Vis (CHCl ₃ ): λ _max (E _rel ) = 329.4 (0.72), 435.4 (0.81), 464.0 (1.00) nm. Fluorescence (CHCl ₃ , λ _exc = 435.0 nm): λ _max (I _rel ) = 473.6 (1.00), 506.4 (0.58) nm. Fluorescence quantum eff. (CHCl ₃ , λ _exc = 435.0 nm, E _{435.0nm / 1cm} = 0.0318, reference: 3 with Φ = 1.00): 0.21. MS (FAB ⁺ ): m / z (%): 751.5 (20) [M + H] ⁺ , 681.4 (5), 624.2 (3), 497.9 (5), 486.9 (100), 415.0 (46), 343.1 (12), 266.3 (24), 168.2 (3), 139.2 (9), 125.2 (22), 111.2 (44), 97.2 (85), 83.2 (98). HRMS (C ₄₇ H ₄₅ NO ₈ ): Ber. m / z: 751.3145, Gef. m / z: 751.3149; Δ = -0.0004.

2- (1-hexylheptyl) -1H-benzo [8,9] furo [3 ', 4': 4,5] pyreno [2,1,10-def] isoquinoline-1,3,11,13 (2H) -tetraone (19) [10]: 2- (1-hexylheptyl) -1H-benzo [10.5] anthra [2,1,9-def] isoquinoline-1,3 (2H) -dione (18) (603 mg, 1.20 mmol) and maleic anhydride (100 g, 1.02 mol) were stirred at 105 ° C until homogeneous melt, with chloroanil (589 mg, 2.39 mmol), stirred for 7 d at 145 ° C and after the 3rd, 4th ., 5th and 6 Day each additional chloranil (147 mg, 0.599 mmol) was added, after cooling, still liquid in acetone (50 mL) dispersed, added to 2 M aqueous HCl (300 mL), stirred for 1 h at room temperature , aged for 1 h, filtered off with suction with a D4 glass frit, dried at 110 ° C. for 16 h, purified by column chromatography (silica gel, CHCl ₃ , for the separation of educt residues and then eluted with CHCl ₃ / glacial acetic acid 20: 1, intense green fluorescent band ), precipitated from a little chloroform with methanol, filtered off with suction (D4 glass frit) and dried at 110 ° C. for 16 h. Y. 646 mg (90.3%, 1.08 mmol) orange solid, mp> 300 ° C. R _f (silica gel, chloroform / glacial acetic acid 20: 1) = 0.75. ¹ H-NMR (600 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.84 (t, ³ J (H, H) = 7.0 Hz, 6H, 2 x CH ₃ ), 1.22-1.49 (m, 16H , 8 × CH ₂ ), 1.96-2.03 (m, 2H, β-CH ₂ ), 2.32-2.41 (m, 2H, β-CH ₂ ), 5.27-5.36 (m, 1H, NCH), 8.35 (t, ³ J (H, H) = 7.7 Hz, 1H, CH _{benzoperylene} ), 8.43 (d, ³ J (H, H) = 8.8 Hz, 1H, CH _{benzoperylene} ), 8.50 (d, ³ J (H, H) = 7.6 Hz, 1H, CH _{benzoperylene} ), 9.04-9.16 (m, 2H, 2 x CH _{benzoperylene} ), 9.23-9.28 (m, 2H, 2 x CH _{benzoperylene} ), 10.02 (s, 1H, CH _{benzoperylene} ) ppm. MS (DEP / EI): m / z (%): 597.2 (20) [M] ⁺ , 580.2 (3), 454.0 (1), 428.0 (5), 415.0 (100), 398.0 (6), 343.0 ( 27), 299.1 (7), 261.1 (1), 157.7 (3), 83.2 (2), 55.1 (7). HRMS (C ₃₉ H ₃₅ NO ₅ ): Ber. m / z: 597.2515, Gef. m / z: 597.2516; Δ = -0.0001.

2- (1-nonyldecyl) -1H-benzo [8,9] furo [3 ', 4': 4,5] pyreno [2,1,10-def] isoquinoline-1,3,11,13 (2H) Tetra (21): 2- (1-nonyldecyl) -1H-benzo [10.5] anthra [2,1,9-def] isoquinoline-1,3 (2H) -dione (20, 600 mg, 1.02 mmol ) and maleic anhydride (100 g) were stirred at 105 ° C until homogeneous melt, with chloroanil (502 mg, 2.04 mmol), stirred for 7 d at 145 ° C and after the 3rd, 4th, 5th and 6. Additional chloranil (125 mg, 0.510 mmol) was added in each case, after cooling still liquid in acetone (50 ml) dispersed, added to 2 M aqueous HCl (400 ml), stirred for 1 h at room temperature, left over 2 h old, filtered off with suction using a D4 glass frit, dried at 110 ° C. for 16 h, purified by column chromatography (silica gel, CHCl ₃ , for the separation of educt residues and then eluted with CHCl ₃ / glacial acetic acid 20: 1, intensively green fluorescent band), from a little chloroform with methanol precipitated (D4 glass frit) and dried at 110 ° C. for 16 h. Y. 680 mg (97.7%, 1.00 mmol) of brown solid, mp> 300 ° C. R _f (silica gel, chloroform / glacial acetic acid 20: 1) = 0.80. ¹ H-NMR (800 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.84 (t, ³ J (H, H) = 7.0 Hz, 6H, 2 x CH ₃ ), 1.19-1.57 (m, 28H , 14 × CH ₂ ), 2.04-2.13 (m, 2H, β-CH ₂ ), 2.36-2.45 (m, 2H, β-CH ₂ ), 5.33 (tt, ³ J (H, H) = 9.0 Hz, ³ J (H, H) = 5.9 Hz, 1H, NCH), 8.14 (d, ³ J (H, H) = 8.5 Hz, 1H, CH _{benzoperylene} ), 8.26 (t, ³ J (H, H) = 7.4 Hz, 1H, CH _{benzoperylene} ), 8.34 (d, ³ J (H, H) = 7.4 Hz, 1H, CH _{benzoperylene} ), 8.63 (d, ³ J (H, H) = 8.0 Hz, 1H, CH _{benzoperylene} ), 8.92-9.07 (m, 3H, 3 x CH _{benzoperylene} ), 9.53 (s, 1H, CH _{benzoperylene} ) ppm. MS (DEP / EI): m / z (%): 681.64 (57) [M] ⁺ , 664.6 (6), 554.4 (4), 510.2 (3), 428.2 (7), 416.2 (100), 343.2 (34), 299.2 (4), 43.0 (4). HRMS (C ₄₅ H ₄₇ NO ₅ ): Ber. m / z: 681.3454, Gef. m / z: 681.3433; Δ = 0.00017.

2,13-bis (1-hexylheptyl) -benzo [6,7] furo [3 ', 4': 4,5] pyrrolo [3 ', 4': 10,11] peryleno [2,1,12-defg] isoquinoline-1,3,5,7,12,14 (2H, 13H) -hexaone (23): 2,12-bis (1-hexylheptyl) benzo [8,9] pyrrolo [3 ', 4': 4, 5] pyreno [2,1,10-def] isoquinoline-1,3,11,13 (2H, 12H) -tetraone (22, 400 mg, 0.513 mmol) and maleic anhydride (50.0 g, 0.510 mol) were at 105 ° Stirred until the homogeneous melt, with chloroanil (252 mg, 1.03 mmol), stirred for 7 d at 190 ° C and after the 3rd, 4th, 5th and 6th Day each additional chloranil (63 mg, 0.257 mmol After cooling, it was still dispersed in liquid acetone (50 mL), to 2 M aqueous HCl (400 mL). The mixture was stirred for 3 h at room temperature, left for 1 h, filtered off with suction with a D4 glass frit, dried at 110 ° C. for 16 h, purified by column chromatography (silica gel, CHCl ₃ , to remove educt residues and then with CHCl ₃ / glacial acetic acid 20: 1 eluted for the separation of by-products and again with CHCl ₃ / methanol 40: 1, intensely green fluorescent band), from glacial acetic acid with methanol / water 1: 1 precipitated, filtered off with suction (D4 glass frit) and dried at 110 ° C for 16 h. Y. 103 mg (23.0%, 0.118 mmol) ocher solid, mp> 300 ° C. R _f (silica gel, chloroform / glacial acetic acid 20: 1) = 0.86. IR (ATR): v ~ = 2953 (m), 2924 (m), 2855 (m), 1842 (vw), 1763 (w), 1705 (vs), 1664 (s), 1603 (m), 1501 ( w), 1445 (m), 1396 (s), 1368 (vs), 1313 (s), 1283 (m), 1241 (m), 1191 (m), 1170 (m), 1115 (w), 1083 ( w), 941 (w), 910 (w), 857 (m), 840 (m), 812 (m), 774 (m), 751 (m), 724 (m), 664 (m) cm ^-1 , ¹ H-NMR (600 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.78-0.92 (m, 12H, 4 x CH ₃ ), 1.17-1.59 (m, 32H, 16 x CH ₂ ), 1.93- 2.03 (m, 2H, β-CH ₂ ), 2.05-2.15 (m, 2H, β-CH ₂ ), 2.36-2.45 (m, 2H, β-CH ₂ ), 2.46-2.57 (m, 2H, β-) CH ₂ ), 4.52-4.65 (m, 1H, NCH), 5.41-5.54 (m, 1H, NCH), 9.12-9.31 (m, 2H, 2 x CH _coronene ), 9.76-9.94 (m, 1H, CH _coronene ), 10.21-10.36 (m, 1H, CH _coronene ), 10.56-10.72 (s, 1H, CH _coronene ), 11.04-11.21 (s, 1H, CH _coronene ) ppm. ¹³ C-NMR (150 MHz, _CDCl3, 27 ° C, TMS): δ = 14.0, 14.1, 22.6, 22.7, 26.9, 27.1, 29.1, 29.3, 29.3, 29.7, 31.8, 31.8, 31.9, 32.5, 32.9 ppm , UV / Vis (CHCl ₃ ): λ _max (E _rel ) = 368.8 (1.00), 431.6 (0.14), 456.8 (0.11), 490.0 (0.07) nm. Fluorescence (CHCl ₃ , λ _exc = 457.0 nm): λ _max (I _rel ) = 491.9 (1.00), 526.4 (0.64), 566.6 (0.32) nm. Fluorescence quantum eff. (CHCl ₃ , λ _exc = 457.0 nm, E _{457 nm / 1 cm} = 0.0017, reference: 3 with 0 = 1.00): 0.07. MS (FAB ^- ): m / z (%): 872.0 (7) [M] ^- , 802.0 (2), 612.7 (3). HRMS (C ₅₆ H ₆₀ N ₂ O ₇ ): Ber. m / z: 872.4401, Gef. m / z: 872.4432; Δ = -0.0031.

13- (4-bromophenyl) -2- (1-nonyldecyl) benzo [6,7] furo [3',4 ': 4,5] pyrrolo [3', 4 ': 10,11] peryleno [2,1- , 12-defg] isoquinoline-1,3,5,7,12,14 (2H, 13H) -hexaone (25): 12- (4-bromophenyl) -2- (1-nonyldecyl) benzo [8,9] pyrrolo [3 ', 4': 4,5] pyreno [2,1,10-def] isoquinoline-1,3,11,13 (2H, 12H) -tetraone (24, 1.05 g, 1.26 mmol) and maleic anhydride ( 125 g) were stirred at 105 ° C until the homogeneous melt, with chloroanil (618 mg, 2.51 mmol), stirred for 7 d at 190 ° C and after the 3rd, 4th, 5th and 6th day each further Chloranil (154 mg, 0.628 mmol), after cooling still liquid in acetone (50 mL), added to 2 M aqueous HCl (400 mL), stirred for 3 h at room temperature, aged over 2 h, with a D4 Glass frit filtered off with suction, dried at 110 ° C. for 16 h, purified by column chromatography (silica gel, CHCl ₃ , to remove educt residues and then with CHCl ₃ / glacial acetic acid 20: 1), precipitated from glacial acetic acid with methanol / water 1: 1, filtered off with suction (D4). Glass frit) and 16 h at 110 ° C dried. Y. 173 mg (14.8%, 0.186 mmol) ocher solid, mp> 300 ° C. R _f (silica gel, CHCl ₃ / MeOH 40: 1) = 0.58. IR (ATR): v ~ = 2924 (m), 2854 (w), 1770 (w), 1713 (s), 1661 (m), 1602 (m), 1492 (m), 1444 (m), 1377 ( vs), 1317 (m), 1244 (m), 1200 (m), 1200 (m), 1177 (m), 1160 (m), 1120 (m), 1089 (m), 1074 (m), 1012 ( m), 939 (w), 857 (m), 840 (m), 811 (m), 773 (m), 766 (m), 753 (m), 720 (m), 657 (m) cm ^-1 , UV / Vis (CHCl ₃ ): λ _max (E _rel ) = 368.8 (1.00), 432.6 (0.21), 456.2 (0.18), 491.0 (0.15) nm. Fluorescence (CHCl ₃ , λ _exc = 456.0 nm): λ _max (I _rel ) = 498.4 (1.00), 527.9 (0.95) nm. Fluorescence quantum eff. (CHCl ₃ , λ _exc = 456.0 nm, E _{456 nm / 1 cm} = 0.0046, reference: 3 with Φ = 1.00): 0.02. MS (FAB ^- ): m / z (%): 930.9 [M + 2H] ^- , 928.9 [M] ^- , 860.0. HRMS (C ₅₅ H ₄₉ BrN ₂ O ₇ ): Ber. m / z: 928.2723, Gef. m / z: 928.2628; Δ = 0.0095.

11- (1-Hexylheptyl) -3H-isobenzofuro [4 ', 5'6', 7 ': 6,7] peryleno [1,12-efg] isoindole-3,5,10,12 (11H) -tetraone ( 27): 2- (1-Hexylheptyl) -1H-peryleno [1,12-efg] isoindole-1,3 (2H) -dione (26, 480 mg, 0.910 mmol) and maleic anhydride (90.0 g) were added at 105 ° Stirred until the homogeneous melt, with chloroanil (447 mg, 1.82 mmol), stirred for 7 d at 145 ° C and after the 3rd, 4th, 5th and 6th Day each additional chloranil (112 mg, 0.455 mmol added, after cooling still liquid in acetone (50 mL), added to 2 M aqueous HCl (400 mL), stirred for 1 h at room temperature, left for 2 h aged, sucked with a D4 glass frit, 16 h at 110 dried ° C, purified by column chromatography (silica gel, CHCl _3, for the separation of Eduktresten and then with _CHCl3 / glacial acetic acid 20: 1 eluted), precipitated from glacial acetic acid with methanol, suction filtered (D4 frit) and 16 h at 110 ° C dried. Y. 182 mg (32.2%, 0.293 mmol) yellow solid, mp> 300 ° C. R _f (silica gel, chloroform / glacial acetic acid 20: 1) = 0.75. IR (ATR): v ~ = 2952 (w), 2925 (w), 2852 (w), 1835 (w), 1761 (s), 1698 (s), 1618 (w), 1555 (w), 1502 ( w), 1466 (m), 1392 m, 1365 m, 1352 m, 1332 m, 1295 m, 1239 m, 1184 m, 1145 m, 1096 m w), 979 (m), 942 (w), 900 (m), 855 (vs), 834 (w), 795 (m), 786 (m), 771 (w), 756 (w), 741 ( m), 733 (m), 657 (m) cm ^-1 . ¹ H-NMR (600 MHz, _CDCl3, 27 ° C, TMS): δ = 0.84 (t, ³ J (H, H) = 7.1 Hz, 6H, 2 × CH _3), 1.24-1.65 (m, 16H , 4 × CH ₂ ), 1.93-2.03 (m, 2H, β-CH ₂ ), 2.34-2.43 (m, 2H, β-CH ₂ ), 4.57 (tt, ³ J (H, H) = 10.1 Hz, ³ J (H, H) = 5.2 Hz, 1H, NCH), 9.11 (d, ³ J (H, H) = 8.5 Hz, 2H, 2 x CH _coronene ), 9.13 (d, ³ J (H, H) = 8.6 Hz, 2H, 2 × CH _coronene ), 9.84 ( ³ J (H, H) = 8.5 Hz, 2H, 2 × CH _coronene ), 10.24 (d, ³ J (H, H) = 8.6 Hz, 2H, 2 × CH _coronene ) ppm. ¹³ C-NMR (150 MHz, _CDCl3, 27 ° C, TMS): δ = 14.1, 22.7, 27.1, 29.4, 29.7, 31.9, 33.0, 124.3, 129.6, 130.1 ppm. UV / Vis (CHCl ₃ ): λ _max (E _rel ) = 339.8 (1.00), 429.0 (0.08), 456.0 (0.09), 485.2 (0.20) nm. Fluorescence (CHCl ₃ , λ _exc = 456.0 nm): λ _max (I _rel ) = 490.3 (1.00), 524.9 (0.39), 563.5 (0.10) nm. Fluorescence quantum eff. (CHCl ₃ , λ _exc = 456.0 nm, E _{456 nm / 1 cm} = 0.0019, reference: 3 with Φ = 1.00): 0.41. MS (DEP / EI): m / z (%): 621.3 (30) [M] ⁺ , 536.0 (44), 466.0 (3), 452.0 (100), 439.0 (17), 397.0 (6), 367.0 ( 12), 323.0 (3), 296.0 (13), 190.1 (4), 148.1 (9), 69.1 (4), 55.1 (9), 44.1 (14). HRMS (C ₄₁ H ₃₅ NO ₅ ): Ber. m / z: 621.2515, Gef. m / z: 621.2514; Δ = 0.0001.

11- (1-nonyldecyl) -3H-isobenzofuro [4 ', 5', 6 ', 7': 6,7] peryleno [1,12-efg] isoindole-3,5,10,12 (11H) -tetraon (29): 2- (1-nonyldecyl) -1H-peryleno [1,12-efg] isoindole-1,3 (2H) -dione (28, 400 mg, 0.654 mmol) and maleic anhydride (65.0 g) were found at 105 ° C stirred to homogeneous melt, with chloranil (321 mg, 1.31 mmol) stirred, stirred for 7 d at 190 ° C and after the 3rd, 4th, 5th and 6th Day each additional chloranil (80 mg, 0.326 mmol) was added, after cooling, still liquid in acetone (50 mL) dispersed, to 2 M aqueous HCl (400 mL), stirred for 1 h at room temperature, allowed to stand for 2 h, filtered off with suction with a D4 glass frit, 16 h at 110 ° C, purified by column chromatography (silica gel, CHCl ₃ , to remove educt residues and then eluted with CHCl ₃ / glacial acetic acid 20: 1), precipitated from glacial acetic acid with methanol, filtered off with suction (D4 glass frit) and dried at 110 ° C. for 16 h. Y. 306 mg (66.3%, 0.433 mmol) of brown solid, mp> 300 ° C. R _f (silica gel, chloroform / glacial acetic acid 20: 1) = 0.88. IR (ATR): v ~ = 2922 (m), 2853 (m), 1941 (vw), 1836 (m), 1759 (vs), 1697 (vs), 1618 (w), 1555 (w), 1501 ( m), 1465 (w), 1409 (w), 1392 (m), 1363 (s), 1350 (s), 1331 (s), 1294 (m), 1236 (m), 1215 (w), 1184 ( s), 1144 (m), 1090 (m), 969 (w), 900 (s), 854 (vs), 833 (m), 796 (m), 785 (m), 769 (m), 754 ( m), 741 (m), 733 (s), 680 (w) cm ^-1 . ¹ H-NMR (800 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.84 (t, ³ J (H, H) = 7.0 Hz, 6H, 2 x CH ₃ ), 1.20-1.70 (m, 28H , 14 × CH ₂ ), 2.04-2.13 (m, 2H, β-CH ₂ ), 2.45-2.53 (m, 2H, β-CH ₂ ), 4.63 (tt, ³ J (H, H) = 10.1 Hz, ³ J (H, H) = 5.2 Hz, 1H, NCH), 8.32 (d, ³ J (H, H) = 8.2 Hz, 2H, 2 × CH _coronene ), 8.57 (d, ³ J (H, H) = 8.0 Hz, 2H, 2 × CH _coronene ), 8.82 (d, ³ J (H, H) = 6.4 Hz, 2H, 2 × CH _coronene ), 9.84 (d, ³ J (H, H) = 7.9 Hz, 2H, 2 x CH _coronene ) ppm. ¹³ C-NMR (101 MHz, _CDCl3, 27 ° C, TMS): δ = 14.1, 22.7, 27.1, 29.4, 29.6, 29.7, 29.7, 31.9, 32.9, 53.0, 119.0, 121.0, 122.7, 122.8, 122.9, 123.2, 123.8, 125.1, 125.4, 128.7, 129.8, 162.9, 169.9 ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 340.0 (1.00) 407.8 (0.67) 429.4 (0.08) 455.6 (12:09), 485.6 (12:19) nm Fluorescence (CHCl _3, λ _exc = 456.0. nm): λ _max (I _rel ) = 490.3 (1.00), 523.9 (0.38) nm. Fluorescence quantum eff. (CHCl ₃ , λ _exc = 456.0 nm, E _{456 nm / 1 cm} = 0.0044, reference: 3 with Φ = 1.00): 0.42. MS (DEP / EI): m / z (%): 705.6 (37) [M] ⁺ , 578.4 (34), 466.2 (3), 452.2 (100), 439.2 (21), 367.2 (11), 296.2 ( 6), 148.0 (2), 83.1 (4), 43.0 (11). HRMS (C ₄₇ H ₄₇ NO ₅ ): Ber. m / z: 705.3454, Gef .: 705.3446; Δ = 0.0008.

Naphtho [2 ', 1', 8 ': 3,4,5] pyreno [1,2-c] furan-1,3-dione (31): perylene (30, 0.400 g, 1.59 mmol) and maleic anhydride (133 g) were stirred at 105 ° C until homogeneous melt, with chloroanil (780 mg, 3.17 mmol), stirred for 2 h at 190 ° C, after cooling, still liquid in acetone (50 mL) dispersed, to 2 M aqueous HCl (400 mL), stirred for 30 min at room temperature, filtered off with suction with a D4 glass frit, washed several times with hot toluene and boiling chloroform and dried at 110 ° C for 16 h. Y. 437 mg (86.1%, 1.37 mmol), red-brown solid, mp> 300 ° C. IR (ATR): v ~ = 1832 (m), 1817 (m), 1795 (m), 1762 (vs), 1601 (w), 1583 (w), 1529 (w), 1504 (w), 1487 ( w), 1446 (vw), 1421 (vw), 1390 (w), 1342 (w), 1327 (m), 1290 (s), 1251 (w), 1223 (m), 1214 (m), 1202 ( w), 1180 (s), 1155 (w), 1146 (m), 1091 (w), 998 (w), 943 (vw), 922 (m), 910 (s), 828 (vs), 820 ( m), 793 (m), 776 (w), 766 (s), 742 (m), 730 (m), 659 (m) cm ^-1 . MS (EI): m / z (%): 346.1 (92) [M] ⁺ , 274.10 (100), 246.1 (2), 173.1 (4), 137.0 (56), 124.2 (4), 44.1 (4) , HRMS (C ₂₄ H ₁₀ O _3): Calcd. m / z: 346.0630, Gef. m / z: 346.0614; Δ = 0.0026.

N, N ', N''- Tris (1-hexylheptyl) -2,5-diphenyl (benzo [ghi] bisimidazolo [4,5-a: 5,4-o) perylene-7,8,10,11, 13,14-hexacarboxylic acid-7,8: 10,11: 13,14-trisdicarboximide (9a): N, N'-bis (1-hexylheptyl) -2,5-diphenyl (benzo [ghi] bisimidazolo [4,5 -a: 5,4-o) perylene-7,8,10,11,13,14-hexacarboxylic acid 10,11-anhydride-7,8: 13,14-bisdicarboximide (9, 70.0 mg, 0.065 mmol), 1-Hexylheptylamine (52.0 mg, 0.259 mmol), imidazole (3.00 g) and toluene (1.0 mL) were stirred for 5 h at 140 ° C, after cooling with 2 M aqueous HCl (30 mL), stirred for 16 h at room temperature , filtered off with suction (D4 glass frit) several times with 2 M HCl, taken up in CHCl ₃ , shaken with 2 M hydrochloric acid, dried over MgSO ₄ , purified by column chromatography with exclusion of light (silica gel, CHCl ₃ , first violet, bright orange fluorescent band) precipitated a little CHCl ₃ with methanol, filtered off with suction (D4 glass frit) and dried at 110 ° C. for 16 h. Y. 37.0 mg (45.3%, 0.029 mmol) of red solid, mp> 300 ° C. R _f (silica gel, chloroform) = 0.60. IR (ATR): v ~ = 3385 (w), 2954 (m), 2923 (s), 2855 (m), 2360 (w), 1760 (w), 1706 (vs), 1644 (s), 1632 ( m), 1568 (w), 1547 (w), 1530 (w), 1483 (w), 1457 (s), 1400 (s), 1349 (s), 1315 (s), 1234 (m), 1201 ( m), 1118 (m), 1027 (w), 941 (m), 917 (w), 888 (m), 813 (m), 770 (m), 761 (m), 723 (m), 705 ( m), 691 (s), 684 (s), 668 (m) cm ^-1 . ¹ H-NMR (600 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.78-0.87 (m, 18H, 6 x CH ₃ ), 1.17-1.59 (m, 48H, 24 x CH ₂ ), 1.85- 1.94 (m, 2H, β-CH ₂ ), 1.97-2.15 (m, 4H, 2 x β-CH ₂ ), 2.31-2.61 (m, 6H, 3 x β-CH ₂ ), 4.51 (tt, ³ J (H, H) = 10.2 Hz, ³ J (H, H) = 5.1 Hz, 1H, NCH), 5:27 to 5:50 (m, 2H, 2 x NCH), 7:33 to 7:49 (m, 2H, 2xCH _aryl ), 7.52-7.61 (m, 1H, CH _aryl ), 7.68 (t, ³ J (H, H) = 7.5 Hz, 2H, 2 x CH _aryl ), 7.79 (t, ³ J (H, H) = 7.4 Hz, 1H, CH _aryl ), 8.18-8.29 (m, 2H, 2 x CH _aryl ), 8.31-8.49 (m, 2H, 2 x CH _aryl ), 10.69 (s, 2H, 2 x CH _{benzoperylene} ), 12.34 ( s, 2H, 2 × NH) ppm. ¹³ C-NMR (150 MHz, _CDCl3, 27 ° C, TMS): δ = 14.0, 22.6, 26.9, 27.3, 29.1, 29.3, 29.5, 29.7, 31.8, 31.9, 32.5, 32.8, 52.9, 55.2, 126.0, 126.1, 127.5, 128.5, 128.7, 128.9, 129.8, 131.3, 132.4, 152.9, 168.8 ppm. UV / Vis (CHCl _3). Λ _max (ε) = 313.0 (113300) 420.6 (130900) 442.4 (78200) 529.6 (145000) 566.2 (169400) nm Fluorescence (CHCl _3, λ _exc = 530.0 nm ). λ _max (I _rel) = 581.0 (1.00) 630.4 (0.50) nm Fluoreszenzquantenausb. (CHCl ₃ , λ _exc = 530.0 nm, E _{530.0nm / 1cm} = 0.0369, reference: 3 with Φ = 1.00): 0.55. MS (DEP / EI): m / z (%): 1263 (60) [M + H] ⁺ , 1262.0 (26) [M] ⁺ , 898.2 (22), 742.8 (29), 716.9 (95), 700.9 (17), 633.9 (8). HRMS (C ₈₂ H ₉₆ N ₇ O ₆ ): Ber. m / z: 1262.7422, Gef. m / z: 1262.7386; Δ = 0.0036. C ₈₁ H ₉₅ N ₇ O ₆ (1262.7): Ber. C 77.05 H 7.58 N 7.77; Gef. C 77.33 H 7.64 N 7.44.

2,6,13-Tris (1-hexylheptyl) -1H-benzo [6,7] dipyrrolo [3 ', 4': 4,5; 3 '', 4 ': 10,11] peryleno [2,1- , 12-defg] isoquinoline-1,3,5,7,12,14 (2H, 6H, 13H) -hexaone (23a): 2,13-di (1-hexylheptyl) benzo [6,7] furo [3 ', 4': 4,5] pyrrolo [3 ', 4': 10,11] peryleno [2,1,12-defg] isoquinoline-1,3,5,7,12,14 (2H, 13H) - hexaone (23, 34.0 mg, 0.039 mmol), 1-hexylheptylamine (31.0 mg, 0.156 mmol), imidazole (2.00 g) and toluene (1.0 mL) were stirred at 140 ° C for 5 h, washed with 2 M aqueous HCl (20 mL ), stirred at room temperature for 16 h and extracted several times with chloroform, washed with 2M aqueous HCl, dried over MgSO ₄ , purified by column chromatography with exclusion of light (silica gel, isohexane / CHCl ₃ 3: 2, second, intensely green fluorescent band), in Vacuum to dryness and dried at 110 ° C for 16 h. Y. 20.0 mg (48.7%, 0.019 mmol) of brownish yellow solid, mp 94 ° C. R _f (silica gel, chloroform / isohexane 2: 3) = 0.67. IR (ATR): v ~ = 3071 (vw), 2954 (m), 2921 (s), 2853 (m), 1880 (vw), 1761 (m), 1702 (vs), 1666 (s), 1619 ( w), 1593 (w), 1498 (w), 1461 (m), 1447 (m), 1408 (m), 1393 (m), 1365 (vs), 1357 (vs), 1311 (vs), 1269 ( m), 1241 (m), 1217 (m), 1181 (m), 1146 (w), 1093 (m), 944 (m), 889 (w), 859 (m), 812 (m), 796 (m) m), 774 (s), 749 (m), 723 (m), 678 (m) cm ^-1 . ¹ H-NMR (600 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.83 (t, ³ J (H, H) = 7.1 Hz, 12H, 4 x CH ₃ ), 0.87 (t, ³ J ( H, H) = 7.0 Hz, 6H, 2 x CH ₃ ), 1.16-1.58 (m, 48H, 24 x CH ₂ ), 1.94-2.02 (m, 4H, 2 x β-CH ₂ ), 2.02-2.10 ( m, 2H, β-CH ₂ ), 2.36-2.45 (m, 4H, 2 x β-CH ₂ ), 2.48-2.57 (m, 2H, β-CH ₂ ), 4.56 (t, ³ J (H, H ) = 10.1 Hz, ³ J (H, H) = 5.3 Hz, 2H, 2 × NCH), 5.49 (tt, ³ J (H, H) = 9.4 Hz, ³ J (H, H) = 5.7 Hz, 1H , NCH), 9.08 (d, ³ J (H, H) = 8.6 Hz, 2H, 2 x CH _coronene ), 10.06 (d, ³ J (H, H) = 8.5 Hz, 2H, 2 x CH _coronene ), 10.99 (s, 2H, 2 x CH _coronene ) ppm. ¹³ C-NMR (150 MHz, _CDCl3, 27 ° C, TMS): δ = 14.0, 14.1, 22.6, 22.7, 29.1, 29.3, 29.3, 29.7, 30.0, 30.2, 31.7, 31.8, 31.9, 32.5, 32.8, 53.3, 55.6, 124.4, 126.4, 128.4, 169.0 ppm. UV / Vis (CHCl ₃ ): λ _max (E _rel ) = 370.6 (1.00), 461.6 (0.04), 493.2 (0.03) nm. Fluorescence (CHCl ₃ , λ _exc = 462.0 nm): λ _max (I _rel ) = 494.8 (1.00), 510.6 (0.58), 529.0 (0.84), 566.5 (0.39) nm. Fluorescence quantum eff. (CHCl ₃ , λ _exc = 462.0 nm, E _{462.0nm / 1cm} = 0.0027, reference: 3 with Φ = 1.00): 0.11. MS (FAB ⁺ ): m / z (%): 1055.1 (11) [M + H] ⁺ , 872.9 (20), 663.8 (44), 647.8 (26), 465.4 (2), 261.5 (2), 69.2 (100). HRMS (C ₆₉ H ₈₈ N ₃ O ₆ ): Ber. m / z: 1054.6673, Gef. m / z: 1054.6681; Δ = -0.0008.

• [1] H. Langhals, S. Kirner, 'Novel fluorescent dyes by the extension of the core of perylenetetracarboxylic bisimides', Eur. J. Org. Chem. 2000, 365–380 .
• [2] B. Ventura, H. Langhals, B. Böck, L. Flamigni, 'Phosphorescent perylene imides', Chem. Commun. 2012, 48, 4226–4228 .
• [3] L. Flamigni, A. Zanelli, H. Langhals, B. Böck, 'Photophysical and redox properties of perylene bis- and tris- dicarboximide fluorophores with triplet state formation: Transient absorption and singlet oxygen sensitization', J. Phys. Chem. A 2012, 116, 1503–1509 .
• [4] Langhals, 'Chromophores for picoscale optical computers' in K. Sattler (ed.), Fundamentals of picoscience, p. 705–727, Taylor & Francis Inc. CRC Press Inc., Bosa Roca/US 2013; ISBN 13: 9781466505094, ISBN 10: 1466505095 .
• [5] H. Langhals, A. J. Esterbauer, A. Walter, E. Riedle, I. Pugliesi, 'Förster resonant energy transfer in orthogonally arranged chromophores', J. Am. Chem. Soc. 2010, 132, 16777–16782 .
• [6] H. Langhals, 'Control of the interactions in multichromophores: Novel concepts. Perylene bisimides as components for larger functional units', Helv. Chim. Acta 2005, 88, 1309–1343 .
• [7] E. Clar, Polycyclic Hydrocarbons, Vol. 1 und 2, 1. Aufl., Academic Press, London-New York und Springer-Verlag, Berlin-Göttingen-Heidelberg 1964; ISBN 978-3-662-01667-1, ISBN: 978-3-662-01670-1 (Print), eISBN 978-3-662-01665-7, eISBN 978-3-662-01668-8 (Online) .
• [8] (a) E. Clar, Ber. Dtsch. Chem. Ges. 1932, 65, 864–859. (b) E. Clar and M. Zander, J. Chem. Soc. 1957, 4616–4619 .
• [9] H. Langhals, A. Hofer, 'Chromophores arranged as 'magnetic meta atoms': Building blocks for molecular metamaterials', J. Org. Chem. 2013, 78, 5889–5897 .
• [10] H. Langhals, B. Böck, T. Schmid, A. Marchuk, 'Angular benzoperylenetetracarboxylic bisimides', Chem. Eur. J. 2012, 18, 13188–13194 .

N, N ', N'',N''' - Quater (1-hexylheptyl) coronene-1,2,4,5,7,8,10,11-octacarbonsäure-1,2: 4,5: 7, 8: 10,11-terabiscarboximide (5a): A mixture of N, N'-bis (1-hexylheptyl) benzo [ghi] perylene-2,3,8,9,11,12-hexacarboxylic acid-2,3,8 , 9-bis (dicarboximide) -11,12-anhydride and N, N'-bis (1-hexylheptyl) coronene-1,2,4,5,7,8,10,11-octacarboxylic acid 1,2: 7 , 8-bis-anhydride-4,5: 10,11-biscarboximide from the Diels-Alder reaction of 2,9-bis (1-hexylheptyl) anthra [2,1,9-def.6,5,10-d 'e'f'] diisoquinoline-1,3,8,10 (2H, 9H) tetraone with maleic anhydride, (400 mg, 0.471 mmol), 1-hexylheptylamine (376 mg, 1.88 mmol), imidazole (4.00 g) and toluene (1.0 mL) were stirred for 5 h at 140 ° C, after cooling with 2 M aqueous HCl (20 mL), stirred for 16 h at room temperature, extracted several times with chloroform, washed with 2 M aqueous HCl, dried over MgSO ₄ , evaporated in vacuo, chromatographed by column chromatography with exclusion of light (silica gel, isohexane / CHCl ₃ 1: 1 for the separation of N, N ', N''- tris (1-hexylhep tyl) benzo [ghi] perylene-2,3,8,9,11,12-hexacarboxylic acid-2,3,8,9,11,12-tris (dicarboximide); first, intensely green fluorescent band; further chromatography: silica gel, isohexane / CHCl ₃ 3: 2), evaporated to dryness and dried at 110 ° C. for 16 h. Y. 24.0 mg dark brown, highly viscous oil. R _f (silica gel, chloroform / isohexane 1: 2) = 0.71. IR (ATR): v ~ = 2954 (m), 2921 (vs), 2853 (s), 1765 (w), 1713 (s), 1669 (s), 1613 (w), 1492 (w), 1459 ( m), 1412 (m), 1393 (m), 1368 (s), 1350 (s), 1306 (vs), 1260 (w), 1237 (m), 1209 (w), 1178 (w), 1093 ( w), 1020 (w), 969 (w), 946 (m), 893 (w), 815 (m), 800 (w), 768 (m), 722 (m), 663 (w) cm ^-1 , ¹ H-NMR (600 MHz, CDCl ₃ , 27 ° C, TMS): δ = 0.82 (t, ³ J (H, H) = 7.0 Hz, 12H, 4 x CH ₃ ), 0.87 (t, ³ J ( H, H) = 7.1 Hz, 12H, 4 × CH ₃ ), 1.16-1.51 (m, 64H, 32 × CH ₂ ), 1.88-1.97 (m, 4H, 2 × β-CH ₂ ), 1.97-2.0 ( m, 4H, 2 x β-CH ₂ ), 2.32-2.42 (m, 4H, 2 x β-CH ₂ ), 2.42-2.52 (m, 4H, 2 x β-CH ₂ ), 4.57 (t, ³ J (H, H) = 10.2 Hz, ³ J (H, H) = 5.1 Hz, 2H, 2 × NCH), 5.47 (tt, ³ J (H, H) = 9.6 Hz, ³ J (H, H) = 5.7 Hz, 2H, 2 x NCH), 11.20 (s, 4H, 4 x CH _coronene ) ppm. ¹³ C-NMR (150 MHz, _CDCl3, 27 ° C, TMS): δ = 14.0, 14.1, 22.6, 22.7, 26.9, 27.0, 29.1, 29.3, 29.3, 29.7, 30.0, 30.2, 31.7, 31.8, 31.9, 32.5, 32.8, 53.3, 55.6, 124.4, 126.4, 128.4, 169.0 ppm. UV / Vis (CHCl _3): λ _max (E _rel) = 299.0 (0.26), 374.8 (1.00) 413.8 (12:37), 476.2 (0.04) 508.2 (0.07) nm Fluorescence (CHCl _3, λ _exc = 476.0. nm): λ _max (I _rel ) = 491.8 (0.23), 509.4 (1.00), 524.3 (0.24), 546.6 (0.44), 588.8 (0.12) nm. Fluorescence quantum eff. (CHCl ₃ , λ _exc = 476.0 nm, E _{476 nm / 1 cm} = 0.0030, reference: 3 with Φ = 1.00): 0.16. MS (FAB ⁺ ): m / z (%): 1305.2 (10) [M] ⁺ , 1124.1 (19), 1123.0 (10), 942.8 (20), 663.8 (38), 647.8 (44), 577.4 (31 ), 507.4 (21), 355.3 (17), 281.3 (8), 69.2 (81). HRMS (C ₈₄ H ₁₁₃ N ₄ O ₈ ): Ber. m / z: 1305.8558, Gef. m / z: 1305.8503; Δ = 0.0055.

• [1] H. Langhals, S. Kirner, Novel fluorescent dyes by extension of the core of perylenetetracarboxylic bisimides, Eur. J. Org. Chem. 2000, 365-380 ,
• [2] Ventura, H. Langhals, B. Böck, L. Flamigni, 'Phosphorescent perylene imides', Chem. Commun. 2012, 48, 4226-4228 ,
• [3] Flamigni, A. Zanelli, H. Langhals, B. Böck, "Photophysical and redox properties of perylene bis- and tris-dicarboximide fluorophores with triplet state formation: transient absorption and singlet oxygen sensitization", J. Phys. Chem. A 2012, 116, 1503-1509 ,
• [4] Langhals, 'Chromophores for picoscale optical computers' by K. Sattler (ed.), Fundamentals of picoscience, p. 705-727, Taylor & Francis Inc. CRC Press Inc., Bosa Roca / US 2013; ISBN 13: 9781466505094, ISBN 10: 1466505095 ,
• [5] H. Langhals, AJ Esterbauer, A. Walter, E. Riedle, I. Pugliesi, 'Förster resonant energy transfer in orthogonally arranged chromophores', J. Am. Chem. Soc. 2010, 132, 16777-16782 ,
• [6] H. Langhals, 'Control of the interactions in multichromophores: Novel concepts. Perylene bisimides as components for larger functional units', Helv. Chim. Acta 2005, 88, 1309-1343 ,
• [7] E. Clar, Polycyclic Hydrocarbons, Vol. 1 and 2, 1st Ed., Academic Press, London-New York and Springer-Verlag, Berlin-Göttingen-Heidelberg 1964; ISBN 978-3-662-01667-1, ISBN: 978-3-662-01670-1 (print), eISBN 978-3-662-01665-7, eISBN 978-3-662-01668-8 (Online) ,
• [8th] (a) E. Clar, Ber. Dtsch. Chem. Ges. 1932, 65, 864-859. (b) E. Clar and M. Zander, J. Chem. Soc. 1957, 4616-4619 ,
• [9] H. Langhals, A. Hofer, 'Chromophores arranged as' magnetic meta atoms ': Building blocks for molecular metamaterials', J. Org. Chem. 2013, 78, 5889-5897 ,
• [10] H. Langhals, B. Böck, T. Schmid, A. Marchuk, 'Angular benzoperylenetetracarboxylic bisimides', Chem. Eur. J. 2012, 18, 13188-13194 ,

Subject of the invention

• a. A process for the Diels-Alder-Clar reaction for the nuclear expansion of aromatics using maleic anhydride, characterized in that maleic anhydride is used in high excess and elevated reaction temperatures; typically in more than 400 moles per mole of aromatics to be expanded to 1000 mol / mol and preferably at temperatures above 145 ° C to 202 ° C and in suitable media such as nitrobenzene to 211 ° C.
• b. A process for the Diels-Alder-Clar reaction for the nuclear expansion of aromatics using maleic anhydride, characterized in that chloranil is added as flavoring in portions, preferably in two to six portions, and further in considerable excess, preferably from 0.1 mol / mol to 4.0 mol / mol, most preferably from 0.5 mol / mol to 1.0 mol / mol of aromatic to be expanded.
• c. Process for the Diels-Alder-Clar reaction for the nuclear expansion of aromatics using maleic anhydride, characterized in that the reaction is carried out for 3 to 7 days, or even longer, up to for example 14 days, preferably seven days.
• d. A process for the Diels-Alder-Clar reaction for the nuclear expansion of aromatics using maleic anhydride, characterized in that the work-up of the still warm, but largely homogeneous melt by dispersing in acetone.
• e. A process for Diels-Alder-Clar reaction for the nuclear expansion of aromatics using maleic anhydride, characterized in that in the workup aqueous hydrochloric acid is added, preferably 2 molar hydrochloric acid.
• f. The coronene derivatives 32 to 35,
  
  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 or two CH groups can 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 have been replaced by nitrogen atoms can. 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-dis 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 cyano groups or linear alkyl chains having up to 18 carbon atoms, in which a to 6 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 are 1,2-, 1,3- or 1,4-substituted phenyl, 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-disubstituted anthracene residues 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 ⁵ to R ¹⁵ can furthermore independently of one another denote the halogen atoms F, Cl, Br or I,
  
  in particular the anhydrides 5, 23, 25, 27 and 29.
• G. The imidazoloperylene anhydride imides 36 and 37 and pyridazinoperylene anhydride imides 38,
  
  in which the radicals R ¹ to R ^{4 have} the meaning given under f, in particular the Imidazoloperylenanhydridimide 7 and 9 and the derivative 11th
  
  and the imides 4a, 5a, 7a, 9a, 11a and 23a derived therefrom
  
  
• H. Perylene anhydride imides of general formula 39,
  
  in which the radicals R ¹ to R ^{5 have} the meaning given under f, in particular the derivative 17.
  
• i. Use of the substances according to f to h as pigments and colorants for dyeing purposes, also for decorative and artistic purposes, such as. For example, for glues and related colors such as watercolor paints and watercolors and inks for inkjet printers, paper inks, inks, inks and inks and other colors for painting and writing purposes and in paints, 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 zapol lacquer, shellac or qi lacquer (Japanese lacquer or Chinese lacquer or East Asian lacquer), for mass coloration of polymers, examples are materials of polyvinyl chloride, 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, polyvinylacetate, Polyacrylnit ril, polyacrolein, polybutadiene, polychlorobutadiene or polyisoprene or the copolymers of said monomers, for coloring natural substances, examples are paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, Flax or its transformation products such. As the viscose fiber, nitrate silk or copper rayon (rayon), as mordant dyes, z. As for the coloring of natural products, examples include paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their conversion products such. As the viscose fiber, nitrate silk or copper rayon (rayon), preferred salts for pickling are aluminum, chromium and iron salts, as a colorant, for. As for coloring paints, varnishes and other paints, paper inks, inks, inks and other colors for painting and writing purposes, as an addition to other colors in which a particular shade is to be achieved, preferred are particularly bright shades. And use of the substances according to f to h for marking, security and display purposes, especially taking into account their fluorescence, such. B. as dyes or fluorescent dyes for signal colors, preferably for the visual highlighting of logotypes and drawings or other graphic products, for marking signs and other objects and in display elements for many display, reference and marking purposes, in which a particular optical color impression can be achieved is for passive display elements, information and traffic signs, such as traffic lights for security marking purposes, the great chemical and photochemical stability and possibly also the fluorescence of the substances of importance, this is preferred for checks, check cards, banknotes, coupons, documents , Identification papers and the like, in which a special, unmistakable color impression is to be achieved, for marking objects for machine recognition of these objects via the fluorescence, preferably the machine detection of objects for sorting, z. As well as for the recycling of plastics, as fluorescent dyes for machine-readable markings, alphanumeric prints or barcodes are preferred as dyes in ink jet printers in homogeneous solution, preferably as fluorescent ink, 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. As in fluorescent displays, shower tubes or in fluorescent tubes, for tracer purposes, eg. As in biochemistry, medicine, technology and science, here, the dyes may be covalently linked to substrates or on Nebenvalenzen such as hydrogen bonds or hydrophobic interactions (adsorption), as dyes or fluorescent dyes in chemiluminescent systems, eg. B. in chemiluminescent light rods, in Lumineszenzimmunoassays or other Lumineszenznachweisverfahren and as a material for leak testing of closed systems.
• j. Use of the dyes according to f to h as functional materials, such. As in data storage, preferably in optical storage, such as the CD or DVD disks, in OLEDS (organic light-emitting diodes), in photovoltaic systems, as pigments in electrophotography: z. B. for dry copying systems (Xerox process) and laser printers ("Non-Impact Printing"), the frequency conversion of light, z. B. to make short-wave light of longer wavelength, visible light, as a starting material for superconducting organic materials, as fluorescent dyes in scintillators, as dyes or fluorescent dyes in optical light collection systems, such as. As the fluorescent solar collector or fluorescence-activated displays, in liquid crystals for deflecting light, as dyes or fluorescent dyes in cold light sources for light-induced polymerization for the preparation of plastics, as dyes or fluorescent dyes for material testing, eg. As in the manufacture and testing of semiconductor circuits and semiconductor devices, as dyes or fluorescent dyes in photoconductors, as dyes or fluorescent dyes in photographic processes, as dyes or fluorescent dyes as part of a semiconductor integrated circuit, the dyes as such or in conjunction with other semiconductors z. Example, in the form of an epitaxy, as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams, but also as a Q-switch switch and as active substances for nonlinear optics, z. B. for the frequency doubling and frequency tripling of laser light.

figure description

1 , Diels-Alder-Clar reaction of maleic anhydride with perylenetetracarboxylic bisimides.

2 , Diels-Alder-Clar reaction of maleic anhydride with imidazoloperylenetetracarboxylic bisimides.

3 , Diels-Alder-Clar reaction of maleic anhydride with bis-imidazoloperylenetetracarboxylic bisimides.

4 , Diels-Alder-Clar reaction of maleic anhydride with the 4-PTAD adduct 10 of 3.

5 , Diels-Alder-Clar reaction of maleic anhydride with the asymmetrically substituted bisimide 12.

6 , Diels-Alder-Clar reaction of maleic anhydride with the asymmetrically substituted bisimide 14.

7 , Diels-Alder-Clar reaction of maleic anhydride with the perylene anhydride imide 16.

8th , Diels-Alder-Clar reaction of maleic anhydride with the perylene imides 18 and 20.

9 , Diels-Alder-Clar reaction of maleic anhydride with benzoperylenebisimides 22 and 24.

10 , Diels-Alder-Clar reaction of maleic anhydride with benzoperyleneimides 26 and 28.

11 , Diels-Alder-Clar reaction of maleic anhydride with perylene (30).

12 , UV / Vis absorption (solid) and fluorescence spectrum (dashed) of 4 in chloroform compared to 3 (dotted).

13 , UV / Vis absorption spectrum (solid line) of 9 in chloroform compared to 3 (dotted).

14 , UV / Vis absorption spectrum (solid line) of 11 in chloroform compared to 3 (dotted). Pricked: reduced UV range.

15 , UV / Vis absorption (solid line) and fluorescence spectrum (dashed line) of 13 in chloroform compared to 3 (dotted).

16 , UV / Vis absorption spectrum (solid line) of 14 in chloroform compared to 3 (dotted).

17 , UV / Vis absorption (solid) and fluorescence spectrum (dashed) of 15 in chloroform compared to 3 (dotted).

18 , UV / Vis absorbance (solid line) and fluorescence spectrum (dashed) of 17 in chloroform versus 3 (dotted).

19 , UV / Vis absorbance (solid line) and fluorescence spectrum (dashed line) of 23 in chloroform compared to 3 (dotted).

20 , UV / Vis absorption (solid line) and fluorescence spectrum (dashed) of 24 in chloroform compared to 3 (dotted).

21 , UV / Vis absorption (solid) and fluorescence spectrum (dashed) of 25 in chloroform compared to 3 (dotted).

22 , UV / Vis absorption (solid, reduced: dot-dashed) and fluorescence spectrum (dashed) of 26 in chloroform compared to 3 (dotted).

23 , UV / Vis absorption (solid line) and fluorescence spectrum (dashed) of 27 in chloroform versus 3 (dotted). Dash-dot: reduced UV range.

24 , UV / Vis absorbance (solid line) and fluorescence spectrum (dashed) of 28 in chloroform versus 3 (dotted).

25 , UV / Vis absorption (solid, reduced: dot-dashed) and fluorescence spectrum (dashed) of 29 in chloroform compared to 3 (dotted).

26 , UV / Vis absorption (solid) and fluorescence spectrum (dashed) of 4a in chloroform compared to 3 (dotted).

27 , UV / Vis absorption (solid) and fluorescence spectrum (dashed) of 5a in chloroform compared to 3 (dotted).

28 , UV / Vis absorption spectrum (solid) of 7a in chloroform compared to 3 (dotted).

29 , UV / Vis absorption (solid) and fluorescence spectrum (dashed) of 9a in chloroform compared to 3 (dotted).

30 , UV / Vis absorption (solid) and fluorescence spectrum (dashed) of 23a in chloroform compared to 3 (dotted).

QUOTES INCLUDE IN THE DESCRIPTION

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

Cited non-patent literature

• H. Langhals, S. Kirner, Novel fluorescent dyes by extension of the core of perylenetetracarboxylic bisimides, Eur. J. Org. Chem. 2000, 365-380 [0034]
• Ventura, H. Langhals, B. Böck, L. Flamigni, 'Phosphorescent perylene imides', Chem. Commun. 2012, 48, 4226-4228 [0034]
• Flamigni, A. Zanelli, H. Langhals, B. Böck, "Photophysical and redox properties of perylene bis- and tris-dicarboximide fluorophores with triplet state formation: transient absorption and singlet oxygen sensitization", J. Phys. Chem. A 2012, 116, 1503-1509 [0034]
• Langhals, 'Chromophores for picoscale optical computers' by K. Sattler (ed.), Fundamentals of picoscience, p. 705-727, Taylor & Francis Inc. CRC Press Inc., Bosa Roca / US 2013; ISBN 13: 9781466505094, ISBN 10: 1466505095 [0034]
• H. Langhals, AJ Esterbauer, A. Walter, E. Riedle, I. Pugliesi, 'Förster resonant energy transfer in orthogonally arranged chromophores', J. Am. Chem. Soc. 2010, 132, 16777-16782 [0034]
• H. Langhals, 'Control of the interactions in multichromophores: Novel concepts. Perylene bisimides as components for larger functional units', Helv. Chim. Acta 2005, 88, 1309-1343 [0034]
• E. Clar, Polycyclic Hydrocarbons, Vol. 1 and 2, 1st Ed., Academic Press, London-New York and Springer-Verlag, Berlin-Göttingen-Heidelberg 1964; ISBN 978-3-662-01667-1, ISBN: 978-3-662-01670-1 (print), eISBN 978-3-662-01665-7, eISBN 978-3-662-01668-8 (Online) [0034]
• (a) E. Clar, Ber. Dtsch. Chem. Ges. 1932, 65, 864-859. (b) E. Clar and M. Zander, J. Chem. Soc. 1957, 4616-4619 [0034]
• H. Langhals, A. Hofer, 'Chromophore Arranged as' Magnetic Meta-atoms ': Building Blocks for Molecular Metamaterials', J. Org. Chem. 2013, 78, 5889-5897 [0034]
• H. Langhals, B. Böck, T. Schmid, A. Marchuk, 'Angular benzoperylenetetracarboxylic bisimides', Chem. Eur. J. 2012, 18, 13188-13194 [0034]

Claims (10)

A process for the Diels-Alder-Clar reaction for the nuclear expansion of aromatics using maleic anhydride, characterized in that maleic anhydride is used in high excess and elevated reaction temperatures; typically in more than 400 moles per mole of aromatics to be expanded to 1000 mol / mol and preferably at temperatures above 145 ° C to 202 ° C and in suitable media such as nitrobenzene to 211 ° C. A process for the Diels-Alder-Clar reaction for the nuclear expansion of aromatics using maleic anhydride, characterized in that chloranil is added as flavoring in portions, preferably in two to six portions, and further in considerable excess, preferably from 0.1 mol / mol to 4.0 mol / mol, most preferably from 0.5 mol / mol to 1.0 mol / mol of aromatic to be expanded. Process for the Diels-Alder-Clar reaction for the nuclear expansion of aromatics using maleic anhydride, characterized in that the reaction is carried out for 3 to 7 days, or even longer, up to for example 14 days, preferably seven days. A process for the Diels-Alder-Clar reaction for the nuclear expansion of aromatics using maleic anhydride, characterized in that the work-up of the still warm, but largely homogeneous melt by dispersing in acetone. A process for Diels-Alder-Clar reaction for the nuclear expansion of aromatics using maleic anhydride, characterized in that in the workup aqueous hydrochloric acid is added, preferably 2 molar hydrochloric acid. The coronene derivatives 32 to 35,

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 of one another 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 can 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-dis 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 cyano groups or linear alkyl chains having up to 18 carbon atoms, in which a to 6 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 are 1,2-, 1,3- or 1,4-substituted phenyl, 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-disubstituted anthracene residues 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 ⁵ to R ¹⁵ can furthermore independently of one another denote the halogen atoms F, Cl, Br or I,

in which the radicals R ¹ to R ^{4 have} the meaning given under f, in particular the Imidazoloperylenanhydridimide 7 and 9 and the derivative 11th

and the imides 4a, 5a, 7a, 9a, 11a and 23a derived therefrom

The imidazoloperylene anhydride imides 36 and 37 and pyridazinoperylene anhydride imides 38,

in which the radicals R ¹ to R ^{4 have} the meaning given under 6, in particular the Imidazoloperylenanhydridimide 7 and 9 and the derivative 11th

Perylene anhydride imides of general formula 39,

in which the radicals R ¹ to R ^{5 have} the meaning given under 6, in particular the derivative 17.

Use of the substances according to 6 to 8 as pigments and colorants for dyeing purposes, also for decorative and artistic purposes, such as. For example, for glues and related colors such as watercolor paints and watercolors and inks for inkjet printers, paper inks, inks, inks and inks and other colors for painting and writing purposes and in paints, 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 zapol lacquer, shellac or qi lacquer (Japanese lacquer or Chinese lacquer or East Asian lacquer), for mass coloration of polymers, examples are materials of polyvinyl chloride, 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, polyvinylacetate, Polyacrylni tril, polyacrolein, polybutadiene, polychlorobutadiene or polyisoprene or the copolymers of said monomers, for coloring natural substances, examples are paper, wood, straw, or natural fiber materials such as wool, hair, pet hair, bristles, cotton, jute, sisal, hemp, Flax or its transformation products such. As the viscose fiber, nitrate silk or copper rayon (rayon), as mordant dyes, z. As for the coloring of natural products, examples include paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their conversion products such. As the viscose fiber, nitrate silk or copper rayon (rayon), preferred salts for pickling are aluminum, chromium and iron salts, as a colorant, for. As for coloring paints, varnishes and other paints, paper inks, inks, inks and other colors for painting and writing purposes, as an addition to other colors in which a particular shade is to be achieved, preferred are particularly bright shades. And use of the substances according to 3 to 8 for marking, security and display purposes, in particular taking into account their fluorescence, such as. B. as dyes or fluorescent dyes for signal colors, preferably for the visual highlighting of logotypes and drawings or other graphic products, for marking signs and other objects and in display elements for many display, reference and marking purposes, in which a particular optical color impression can be achieved is for passive display elements, information and traffic signs, such as traffic lights for security marking purposes, the great chemical and photochemical stability and possibly also the fluorescence of the substances of importance, this is preferred for checks, check cards, banknotes, coupons, documents , Identification papers and the like, in which a special, unmistakable color impression is to be achieved, for marking objects for machine recognition of these objects via the fluorescence, preferably the machine detection of objects for sorting, z. As well as for the recycling of plastics, as fluorescent dyes for machine-readable markings, alphanumeric prints or barcodes are preferred as dyes in ink jet printers in homogeneous solution, preferably as fluorescent ink, 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. As in fluorescent displays, Braun tubes or in fluorescent tubes, for tracer purposes, eg. As in biochemistry, medicine, technology and science, here, the dyes may be covalently linked to substrates or on Nebenvalenzen such as hydrogen bonds or hydrophobic interactions (adsorption), as dyes or fluorescent dyes in chemiluminescent systems, eg. As in chemiluminescent light rods, in luminescence immunoassays or other luminescence detection method and as a material for leak testing of closed systems. Use of the dyes according to 6 to 8 as functional materials, such. As in data storage, preferably in optical storage, such as the CD or DVD disks, in OLEDS (organic light-emitting diodes), in photovoltaic systems, as pigments in electrophotography: z. B. for dry copying systems (Xerox process) and laser printers ("Non-Impact Printing"), the frequency conversion of light, z. B. to make short-wave light of longer wavelength, visible light, as a starting material for superconducting organic materials, as fluorescent dyes in scintillators, as dyes or fluorescent dyes in optical light collection systems, such as. As the fluorescent solar collector or fluorescence-activated displays, in liquid crystals for deflecting light, as dyes or fluorescent dyes in cold light sources for light-induced polymerization for the preparation of plastics, as dyes or fluorescent dyes for material testing, eg. As in the manufacture and testing of semiconductor circuits and semiconductor devices, as dyes or fluorescent dyes in photoconductors, as dyes or fluorescent dyes in photographic processes, as dyes or fluorescent dyes as part of a semiconductor integrated circuit, the dyes as such or in conjunction with other semiconductors z. Example, in the form of an epitaxy, as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams, but also as a Q-switch switch and as active substances for nonlinear optics, z. B. for the frequency doubling and frequency tripling of laser light.

Images