DE102008058454A1 - Use of an alpha effective compound, and an isoxazolidine compound e.g. as an electron donor group in light-driven systems for charge separation, to extract solar energy, preferably in photovoltaic cells, and for mass coloring of polymers - Google Patents

Abstract

Use of alpha -effective compound (I), and an isoxazolidine compound (II), as an electron donor group in light-driven systems for charge separation, is claimed. Use of alpha -effective compound of formula (X(R 1>)(R 3>)-Y 1>(R 2>)(R 3>)) (I), and isoxazolidine compound of formula (II), as an electron donor group in light-driven systems for charge separation, is claimed. X, Y 1>elements with free, non-binding electron pairs, preferably element from II or III group, N, O, F, S or Cl, preferably elements from II group, N or O; and R 1>-R 5>H, linear 1-37C-alkyl, in which 1-10 CH 2units are optionally substituted by carbonyl, O, S, Se, Te, cis or trans-CH = CH-, and one CH unit is 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 napthalene, in which 1-2 CH-groups are optionally substituted by N, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene in which one or two CH groups are optionally substituted by N, where 2-12 single H atoms of the CH 2-groups are optionally substituted by halo, or CN or a linear 2-18C-alkyl, in which 1-6 CH 2-units are optionally substituted by carbonyl, O, S, Se, Te, cis or trans-CH=CH-groups, in which one CH unit is optionally substituted by N, 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 napthalene in which one or two carbon atoms are optionally substituted by N, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene, in which one or two carbon atoms are optionally substituted by N, where 2-12 single H atoms of the CH 2-group of the alkyl residue is optionally substituted by F, Cl, Br, or CN, or linear 2-18C-alkyl, in which 1-6 CH 2units are optionally substituted by carbonyl, O, S, Se, Te, cis or trans-CH=CH-, in which a CH unit is 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 napthalene, in which one or two carbon atoms are optionally substituted by N, or 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene, in which one or two carbon atoms are optionally substituted by N. Where instead of substituents, the free valency of the methine group and/or quaternary C-atom are pair-wise connected to form rings, e.g. cyclohexane ring, and the residues of R 1>-R 9>are optionally substituted by F, Cl, Br or I. Independent claims are included for: (1) a perylene bisimide-dyaden compound of formula (III); (2) a perylenetetracarboxylic acid bisimide-nitrone compound of formula (IV); (3) the preparation of (III); and (4) the preparation of (IV) comprising reacting perylenebisimide-aldehyde and hydroxylamine derivative, which is N-methyl hydroxylamine or N-phenyl hydroxylamine. R 6>-R 10>R 1>; and X : 1-12 CH 2units, which is optionally substituted by carbonyl, O, S, Se, Te, cis or trans-CH=CH-groups, in which one CH unit is 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 napthalene, in which 1-2 CH groups are optionally substituted by N, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene, in which 1-2 CH groups are optionally substituted by N, where 2-12 single H atoms of CH 2-group are optionally substituted by F, Cl, Br, I or CN, or a linear 2-18C-alkyl, in which 1-6 CH 2-units are optionally substituted by carbonyl, O, S, Se, Te, cis or trans-CH=CH-groups, in which one CH unit is optionally substituted by N, 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 napthalene, in which 1-2C atoms are optionally substituted by N, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene, in which 1-2C atoms are optionally substituted by N, where 2-12 single H of CH 2-group of alkyl residue is optionally substituted by halo, CN or linear 2-18C-alkyl, in which 1-6 CH 2-units are optionally substituted by carbonyl, O, S, Se, Te, cis or trans-CH=CH-groups, in which a CH unit is 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 napthalene, in which 1-2C are optionally substituted by N, or 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 1-2C are optionally substituted by N. Where instead of substituents, the free valency of the methine group and/or quaternary C-atom are pair-wise connected to form rings, e.g. cyclohexane ring, and the residues of R 6>-R 8>are optionally substituted by F, Cl, Br or I. [Image] [Image] [Image].

Description

State of the art

The light - driven separation of electric charges obtained in the fundamental scientific research and in technology a growing one Interest. Here is the prospect of using solar energy efficiently collect and convert into electrical energy. As light-absorbing Structures are organic materials for the future Developments very interesting, because with them strong color Chromophores can be realized that are uncomplicated Modified way within wide limits and to the respective requirements can be adjusted. In addition, let Easily recycle or dispose of organic materials, a point of view for longer-term developments becomes more and more important. So far, however, is only one limited number of such compounds available. The Long term stability of such systems is an unresolved one Problem. A universal, lightfast system for light-induced Generation of charge separation would bring a significant Progress.

task

The Object of the present invention was organic structures to develop, which succeeds in an efficient way a light-driven To achieve charge separation. Here, the light fastness was such Structures of central importance.

description

For Light-driven charge separations require a light-absorbing Unit - in the following called the chromophore - and a structure that causes the charge separation. here we can basically both units are built up from chromophores be, as has been realized in previous work [1]. But here is the fundamental problem that both Chromophores on both light absorption and charge separation have to be optimized; such a question leads often compromises that must be made. In addition, there is the fundamental problem that the extinction coefficients of the Single chromophores need to be coordinated because the chromophores are linked together so that the Light absorption capacity of the final assembly not controlled by the relative concentration of the components can be.

We Therefore, here assume a single chromophore to associate with a colorless structure to charge separation to reach. As chromophores we have the perylene-3,4: 9,10-tetracarboxylic bisimides (1), characterized by their high absorption coefficients, their great light fastness and chemical resistance to distinguish [2]. Their high fluorescence quantum yields [3] of Nearly 100% is an important prerequisite for development of systems with light-driven charge separation, because remains the optical excitation energy for in the sequence received ongoing processes. The nitrogen atoms of 1 are ideal Linkage points for the construction of the other Structure, because here in the for the optical properties important orbital HOMO and LUMO nodes [4] are present with it electronically decouple these substituents from the R residues. There the perylenebisimides 1 are sparingly soluble we for one of the residues R the solubility enhancing 1-hexylheptyl radical ("dovetail radical"; 1a for both radicals R) used [5] and the linkage made to the other functional structures with the second radical R.

For electron transfer after the optical excitation, a high-lying orbital is required, regardless of whether π or n orbital, such. B. like the n-orbital of free amines. The optical excitation creates an electron gap in the HOMO of the dye, which is then filled by the electron transfer from the high orbital of the substituent, so that a return of the excited electron, z. B. under fluorescent light delivery, is impossible. As a result, the fluorescence quenching is the same measured a consequence and a very good indicator of the electron transfer reaction. An amino group bound directly to the carboxylic imide nitrogen leads to fluorescence quenching [6] and confirms this process. However, the amino group and the chromophore are very close to each other, so that the re-transfer is rapid and thus hardly a use of the charge separation is possible. If one brings a spacer between the amino group and the chromophore, then this electron transfer process comes to a complete standstill and the substances fluoresce with almost 100% [7]. It is to be asked if the electron donor properties of the group can be increased so much that the electron transfer is switched on again even with a larger distance. We asked ourselves if one could use the α-effect for this purpose, ie a structure with two directly bound atoms, both of which carry lone pairs of electrons. Here is basically a combination of nitrogen with oxygen of interest. However, such hydroxylamines are relatively labile. The question is whether one can stabilize such a structure by incorporation into a ring. We asked ourselves whether isoxazolidines [8] are suitable structures for this purpose.

We have used as the starting material for such a structure, the aldehyde 2 [9] and this reacted with N-methylhydroxylamine to Methylnitron 3; please refer 1 , Disappointingly, this 1,3-dipole [10] does not react with olefins such as styrene; obviously, the reactivity of the substance is too small for this. In 3, the fluorescence is quenched, so that it already formally meets the conditions for the light-driven charge separation, but here disturbs their lability, because it is reclaimed with water traces of the starting material. Alternatively, by reacting 2 with phenylhydroxylamine, we synthesized the more reactive [11] N-phenyl derivative 4, which now reacted smoothly with an excess of styrene to 5, which was obtained as a difficult-to-separate pair of diastereomers 5a and 5b; see. Ref. [10]. As further examples, the olefins methyl methacrylate and crotonic acid methyl ester were converted to the isoxazolidines 6, and 7, in each of which a diastereomer was obtained; Obviously steric effects come into play here for the control of product formation; please refer 2 , Also acrylonitrile reacts smoothly with 4, but forms the difficult to separate Regioisomerenpaar 8 and 9.

For charge separation over longer distances, an attempt was made to replace the phenyl spacer of 3 by a biphenyl spacer. Although an analogous reaction of 10 with N-methylhydroxylamine to nitrone 11 was possible without problems, no reactions with olefins such as styrene lead to the isoxazolidines. The reactivity of the nitrone is even so small that the substance can be synthesized in styrene as a solvent; please refer 3 , Here was therefore trying to represent the N-phenyl nitrone, from which a higher reactivity is expected. However, this is already so decomposing that its pure representation caused considerable problems. Alternatively, aldehyde 10 was reacted with N-phenylhydroxylamine in the presence of styrene so that the resulting nitrone was trapped directly. In this way it was possible to obtain the isoxazolidine 12 as a diastereomer pair 12a and 12b, the separation of which, however, caused considerable problems. However, extremely similar properties of the two diastereomers are expected, so that a separation for the vast majority of applications is not required.

The UV / Vis absorption spectra of the new nitrone and isoxazolidines are identical in the visible spectral range and deviate only half a nm from the spectrum of dye 1a, which carries two sec-alkyl groups on the nitrogen atoms. In the UV range, the differences are more pronounced; please refer 5 , Thus, the biphenyl spacer contributes significantly to absorption below 300 nm. The differences in the spectra of the other derivatives are also less pronounced in this spectral range, so that the substances are interchangeable from the spectrums. Since the spectra of the various derivatives are virtually identical, one can assume an electronic decoupling of chromophore and functional unit, because otherwise a reaction would have to result.

The fluorescence of isoxazolidine is surprisingly quenched. The efficiency of this quenching is surprising and noteworthy given the strong fluorescence of the amine derivatives mentioned. The fluorescence quenching is attributed to electron transfer from the isoxazolidine moiety, which is electron-rich by the α-effect, to the optically excited perylene moiety; please refer 4 , The HOMO of the electronic ground state, which is only half filled by the optical excitation, is completely filled again by the electron transfer. A return of the excited electron with light emission into its original orbital is thereby suppressed and the fluorescence quenched. Surprisingly, not only is the fluorescence of compounds 5 quenched with a simple phenyl spacer between chromophore and the isoxazolidine moiety, but even at 12 when a biphenyl spacer is present. Here, the distance between electron donor and electron acceptor is already much larger and thus the charge separation takes place over a considerable distance. The electron transfer must be very efficient, because it does not disturb the relatively large distance of the structures involved nor the comparatively low Polarity of the solvent chloroform, in which charges can not be well stabilized by solvation.

The fluorescence quenching of the isoxazolidine derivatives by electron transfer can be clearly differentiated experimentally from predissociation processes as an alternative possibility. When the isoxazolidine 5 is protonated with trifluoroacetic acid or complexed with boron trifluoride etherate, the α-effect interaction is abolished by blocking the lone pair of electrons on the nitrogen atom and, in addition, lowering the position of the nonbonding orbitals of the attached oxygen atom; the strength of the NO bond, however, changes only insignificantly by the protonation. Such protonation turns on the fluorescence of the dye fully, so that this clearly supports a favored by the α-effect electron transfer. Accordingly, the Isoxazoloidine can be 5-6 [8] used as bases with a pK _α even as a fluorescent indicator.

The light-driven charge separation in the oxazolidines is for technical applications extremely interesting, because charge separations not only play a central role in the photosynthetic reaction center Role, but also in systems for photovoltaic energy. The relatively large distance between the separate charges is favorable for another transport for use, because it impedes recombination, which would convert the absorbed energy into heat.

For A technical use in photovoltaics can be structures like 12 z. B. install directly in layer systems. Even more skillful it is, with the help of 1,3-dipolar cycloaddition, the charge-separating structure to fix on a surface. Here you can, for example a metal surface that easily emits electrons, like z. As aluminum, magnesium or calcium, with a styrene derivative occupy an anchor group, such as. B. a carboxylate group. If you now perform the 1,3-dipolar cycloaddition with a perylene nitrone as 4, then the isoxazolidine formed thereby directly on the metal surface [12]. As an alternative can It is also possible to conventionally build up such isoxazolidine with anchor groups and then bring it into contact with a metal surface, so that they are tied there. If you have the metal surface with a more lipophilic medium in contact, then you can expect an increased interaction with this medium. Ideally, the areoxazolidin bound then Chromophores on and protrude into the medium. You would have then Optimal charge separation away from the metal surface and an electrically conductive medium can then take over the charge of the perylene chromophore. Such a photovoltaic system is of particular interest because it is made exclusively in the light-absorbing area Hydrogen, carbon, oxygen and nitrogen exist and Therefore, it can be easily disposed of after use. As light-absorbing structure used perylene dyes are extraordinary lightfast - they are among the most lightfast Fluorescent dyes at all - is having a very long life of the system. Because it is the new Dye systems are easily soluble substances, They can be made from solution on the surfaces be applied. This can be z. By casting, spincoating or else via inkjet printing. With the The latter method also gives you the option of the coverage of the surface in micrometer dimensions too structure. This can be z. B. be advantageous if the photovoltaic power of individual small areas as individual solar cells or of Groups of such solar cells to be dissipated. This can z. B. have the advantage that you can individual cells of the groups can turn off when this z. B. have been broken, without the others to impair. Of particular advantage is the Flexibility of organic materials with which the Solar cell systems on curved surfaces, such as z. B. conventional roof tiles can be adapted; this is pronounced with those now predominantly used brittle inorganic materials hardly possible.

you can also be the light-driven charge separation by the new dyes in the known titanium dioxide solar cells, use in which a Electrolyte is used as a medium, such. B. conventional liquid Electrolytes such as mineral salt-containing liquids, organic liquid electrolytes, such as various imidazolium salts, or also use solid electrolytes, of which the Grätzel cell the best known is. These cells have the problem that the titanium dioxide not in the visible range, but in the UV range absorbed, leaving only a small energy yield during irradiation with sunlight results. Here, auxiliaries are needed absorb them in the longer wavelength range and there the Carry out charge separation. The new oxazolidine derivatives are predestined for such applications.

Finally, the new isoxazolidines can also be combined with conventional silicon solar cells, thus producing multilayer solar cells with organic material. The organic material may be used for efficient light driven carrier injection into the silicon. The achievable high molar absorption coefficient and the problem-free adaptation to various spectral ranges is a particular advantage of a coating with organic material. It should be noted in particular that the organic materials are unproblematic in the production, handling and disposal. It can even be removed from the silicon surface for recycling so that pure silicon can be recovered.

Except In photovoltaic, charge separation can also be used for use chemical reactions. So you can z. B. with the light-induced Radical anions of perylenebisimides achieve chemical reductions; this can be z. B. the complementarily formed positive charge of isoxazolidines via electrodes or others Redeem facilities. To the same extent the isoxazolidine structures are used as the oxidizing agent. In this way, it is possible, for. B. from solar radiation chemical process energy to win.

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-hexylheptyl) -N '- (4-N' '- methylcarbaldimin-N' '- oxidobenzyl) perylene-3,4: 9,10-tetracarboxylic acid bisimide (3):

N- (4-Formylbenzyl) -N '- (1-hexylheptyl) perylene-3,4: 9,10-bis (dicarboximide) (2 [9], 1.10 g, 1.59 mmol), N-methylhydroxylamine hydrochloride (200 mg, 2.39 mmol) and NaHCO ₃ (287 mg, 3.31 mmol) were dissolved in CH ₂ Cl ₂ (50 mL), treated with MgSO ₄ (400 mg), heated at reflux for 5 h, stirred at room temperature for 16 h, filtered, evaporated and purified by column chromatography (silica gel, dichloromethane / methanol 30: 1). Y. 830 mg (65%) of red dye, mp> 300 ° C. R _f (silica gel, dichloromethane / methanol 25: 1) = 0.30. IR (ATR): ν ~ = 2955.4 m, 2919.5 s, 2854.0 m, 1692.4 s, 1647.1 s, 1591.7 s, 1574.5 m, 1505.8 w, 1465.8 w, 1435.8 m, 1402.5 m, 1353.1 m, 1337.1 s, 1250.4 m, 1171.9 m, 1127.2 w, 1109.4 w, 1005.5 w, 982.7 w, 851.2 w, 809.2 s, 744.5 m, 645.2 w cm ^-1 . ¹ H-NMR (600 MHz, CDCl _3, 25 ° C): δ = 0.83 (t, 1H, ³ J = 6.8 Hz), 1:24 to 1:40 (m, 16H, CH _2), 1.88-1.93 (m, 2H , β-CH ₂ ), 2.24-2.30 (m, 2H, β-CH ₂ ), 3.88 (s, 3H, CH ₃ ), 5.16-5.21 (m, 1H, CH-N), 5.42 (s, 2H, CH ₂ -N), 7.33 (s, 1H, CH-N), 7.60 (d, 1H, ³ J = 7.1 Hz), 8.17 (d, 1H, ³ J = 7.1 Hz), 8.57-8.68 ppm (m, 8H, H _pery ). ¹³ C-NMR (150 MHz, CDCl _3, 25 ° C): δ = 14.3, 22.8, 27.2, 29.4, 32.0, 32.6, 43.8, 55.1, 123.1, 123.4, 126.5, 126.6, 128.9, 129.2, 129.6, 129.7, 130.0, 130.2, 131.3, 131.8, 132.0, 134.4, 135.1, 139.6, 163.5 ppm. UV / Vis (CHCl _3): λ _{max (rel} E) = 529 (1.0), 492 (0.60), 463 nm (12:21). MS (DEI ⁺ / 70 eV): m / z (%) = 720 (7) [M ⁺ ], 719 (14), 704 (17), 703 (38), 702 (24), 538 (15), 537 (19), 523 (22), 522 (64), 521 (100), 520 (21), 509 (14), 508 (21), 374 (14), 373 (26), 346 (18), 260 (10), 148 (13). C ₄₆ H ₄₅ N ₃ O ₅ (719.9): Ber. C 76.75, H 6.30, N 5.84; Gen. C 76.69, H 6.24, N 5.66.

N- (1-hexylheptyl) -N '- (4-N' '- phenylcarbaldimin-N' '- oxidobenzyl) perylene-3,4: 9,10-tetracarboxylic acid bisimide (4):

Formylbenzyl) -N '- (1-hexylheptyl) perylene-3,4: 9,10-bis (dicarboximide) [9] (2, 1.10 g, 1.59 mmol) and N-phenylhydroxylamine (200 mg, 1.83 mmol) were added in CH ₂ Cl ₂ (50 mL) dissolved with MgSO ₄ (400 mg), heated under reflux for 5 h, stirred for 16 h at room temperature, filtered, evaporated and purified by column chromatography (silica gel, dichloromethane / methanol 30: 1). Y. 1.15 g (93%) of red dye, mp> 300 ° C. R _f (silica gel, dichloromethane / methanol = 25: 1) = 0.36. IR (ATR): ν ~ = 3066.9 w, 2952.0 m, 2923.4 s, 2854.1 m, 1691.8 s, 1646.1 s, 1592.0 s, 1575.4 m, 1504.9 w, 1483.0 w, 1457.9 w, 1435.6 w, 1402.6 m, 1334.8 s, 1249.0 m, 1170.8 m, 1125.9 w, 1108.1 w, 1069.6 w, 1022.9 w, 987.3 w, 892.3 w, 850.5 w, 832.3 w, 809.6 m, 763.0 w, 684.9 w, 660.6 w, 622.5 w cm ^-1 . ¹ H-NMR (600 MHz, CDCl _3, 25 ° C): δ = 0.83 (t, 1H, ³ J = 6.8 Hz, 6H), 1:24 to 1:40 (m, 16H, CH _2), 1.88-1.93 (m , 2H, β-CH ₂ ), 2.24-2.30 (m, 2H, β-CH ₂ ), 5.16-5.21 (m, 1H, CH-N), 5.37 (s, 2H, CH ₂ -N), 7.43- 7.46 (m, 3H, H _aryl ), 7.66 (d, 1H, ³ J = 8.4 Hz, _aryl ), 7.74 (d, 1H, ³ J = 6.7 Hz, _aryl ), 7.90 (s, 1H, CH- N), 8.24-8.36 ppm (m, 8H, H _pery ). ¹³ C-NMR (150 MHz, CDCl _3, 25 ° C): δ = 14.0, 27.0, 29.2, 31.8, 32.4, 43.5, 54.9, 121.7, 122.7, 122.9, 123.3, 124.1, 125.9, 126.0, 129.0, 129.1, 129.2, 129.3, 129.3, 129.9, 130.1, 130.8, 131.2, 131.6, 133.8, 134.0, 134.4, 139.8, 149.0, 163.0, 163.3 ppm. UV / Vis (CHCl _3): λ _max (ε) = 463 (19600), 492 (53400), 529 nm (84300). MS (EI ⁺ / 70 eV): m / z (%) = 782 (10) [M ⁺ + H], 767 (15), 766 (33), 690 (26), 584 (56), 583 (87 ), 509 (50), 508 (90), 374 (14), 346 (21), 285 (23), 284 (100), 210 (20), 209 (25), 208 (24). C ₄₀ H ₄₁ N ₇ O ₄ (683.8): Ber. C 70.26, H 6.04, N 14.34; Gef. C 69.96, H 5.89; N 14.15;

N- (1-Hexylheptyl) -N '- (4-N' '- methylcarbaldimine-N' '- oxidobiphenyl) perylene-3,4: 9,10-tetracarboxylic bisimide (11):

N- (4-Carboaldehydebiphenyl-4'-methyl) -N '- (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic acid bisimide (10, 100 mg, 0.130 mmol) was dissolved in styrene (5 mL), with N-methylhydroxylamine hydrochloride (109 mg, 1.30 mmol) and sodium bicarbonate (109 mg, 1.30 mmol) and heated to 85 ° C (slight evolution of gas). The precipitated after 30 minutes red solid was filtered off and purified by column chromatography (silica gel, dichloromethane / methanol 30: 1). Two by-products and the starting material are eluted rapidly and then the reaction product as a red band. This was evaporated, dissolved in a little dichloromethane, precipitated with methanol, filtered off and dried at room temperature. Y. 53 mg (51%) of a red solid, mp> 300 ° C. R _f (silica gel, dichloromethane / methanol 30: 1) = 0.14. IR (ATR): ν ~ = 2953.0 m, 2924.3 m, 2855.7 m, 1691.8 s, 1651.9 s, 1592.9 s, 1576.8 m, 1507.4 w, 1495.9 w, 1456.9 w, 1435.7 m, 1403.5 m, 1379.0 w, 1333.6 s, 1248.8 m, 1218.2 w, 1195.3 w, 1169.2 m, 1126.5 m, 1106.7 m, 1003.1 w, 988.4 w, 943.0 w, 853.3 m, 808.0 s, 782.8 m, 748.1 s, 721.2 m, 667.0 w, 639.5 m, 615.4 m , 587.4 m cm ^-1 . ¹ H-NMR (600 MHz, CDCl _3, 25 ° C): δ = 0.82 (t, ³ J _{H, H} = 7.0 Hz, 6H, CH _3), 1:22 to 1:36 (m, 16H, CH _2), 1.85 -1.91 (m, 2H, β-CH ₂ ), 2.22-2.29 (m, 2H, β-CH ₂ ), 3.89 (s, 3H, CH ₃ ), 5.16-5.21 (tt, ³ J _{H, H} = 5.9 Hz, ³ J _{H, H} = 9.3 Hz, 1H, α-CH), 5.42 (s, 2H, CH ₂ -N), 7.38 (s, 1H, CH = N), 7.54-7.61 (m, 8H, H _arom ), 8.48-8.54 ppm (m, 8H, H _perylene ). ¹³ C-NMR (150 MHz, CDCl _3, 25 ° C): δ = 14.0, 22.6, 27.0, 29.2, 29.9, 31.8, 32.4, 43.4, 54.9, 122.9, 123.0, 123.1, 123.2, 127.0, 127.2, 127.5, 127.6, 128.9, 129.3, 129.5, 129.6, 129.7, 129.7, 130.2, 131.6, 131.6, 134.1, 134.8, 134.9, 135.0, 135.2, 136.7, 137.4, 139.0, 139.5, 163.3, 163.4 ppm. UV / Vis (CHCl _3): λ _{max (.} E _rel) = 463 (0.22), 492 (0.61), 529 nm (1.0). HRMS (C ₅₂ H ₄₉ N ₃ O ₅ ): Ber. m / z: 795.369, Gef. m / z: 795.371, Δ = 2 mmu.

N- (1-hexylheptyl) -N'-4- (5-methyloxycarbonyl-5-methyl-2-phenylisoxazolidin-3-yl) benzylperylen-3,4: 9,10-tetracarbonsäurebisimid (6):

N- (1-Hexylheptyl) -N '- (4-N "-phenylcarbaldimine-N" -oxidobenzyl) perylene-3,4: 9,10-tetracarboxylic acid bis-imide (4, 110 mg, 141 μmol) was prepared in Methymethyl acrylate (20 mL), heated to 60 ° C (after 3 h complete solution) allowed to cool, evaporated in vacuo and purified by chromatography (silica gel, CH ₂ Cl ₂ / MeOH 50: 1). Y. 87 mg (70%), mp> 300 ° C. R _f (silica gel, CH ₂ Cl ₂ / MeOH 50: 1) = 0.80. IR (ATR): ν ~ = 2921 m, 2852 m, 1737 w, 1693 s, 1654 s, 1593 s, 1577 m, 1507 W, 1486 W, 1434 W, 1403 m, 1377 W, 1332 s, 1300 W, 1248w, 1201w, 1170w, 1125w, 1101w, 1021w, 981w, 853w, 809m, 743w, 694w cm- ¹ . ¹ H-NMR (600 MHz, CDCl _3, 25 ° C): δ = 0.82 (t, 3H, ³ J = 7.0 Hz, CH _3), 1:19 to 1:38 (m, 16 H, CH _2), 1.61 (s , 3H, CH ₃ ), 1.85-1.91 (m, 2H, β-CH ₂ ), 2.22-2.29 (m, 2H, β-CH ₂ ), 2.27 (dd, 1H, ³ J = 7.4 Hz, ² J = 12.5 Hz), 3.31 (dd, 1H, ³ J = 8.9 Hz, ² J = 12.5 Hz), 3.55 (s, 3H, OCH ₃ ), 5.16-5.21 (m, 1H, α-CH), 4.74 (dd, 1H, ³ J = 7.4 Hz, ³ J = 8.9 Hz), 5:39 (s, 2H, N-CH _2), 6.81-6.83 (m, 1H, H _aryl), 6.89-6.90 (m, 2H, H _aryl) , 7.18-7.13 (m, 2H, H _aryl ), 7.57 (d, 2H, ³ J = 8.4 Hz), 7.43 (d, 2H, ³ J = 8.4 Hz), 8.53 (d, 2H, ³ J = 8.1 Hz , _perylene H), 8:56 (d, 2H, ³ J = 8.1 Hz, H _perylene), 8.62-8.67 ppm (m, 4H, H _perylene). ¹³ C-NMR (150 MHz, CDCl _3, 25 ° C): δ = 14.0, 22.5, 26.9, 29.2, 29.7, 31.8, 32.4, 43.4, 43.4, 49.8, 52.3, 54.8, 69.4, 83.2, 114.5, 117.0, 121.4, 122.9, 123.2, 124.1, 126.3, 126.6, 128.4, 129.6, 131.0, 131.0, 131.6, 134.2, 134.9, 136.4, 140.8, 151.1, 163.4, 164.6, 173.4 ppm. UV / Vis (CHCl ₃ ): λ _max (ε) = 459.1 (18600), 491.0 (51400), 527.4 nm (85800). MS (DEI ⁺ / 70 eV): m / z (%): 690 (33) [M ⁺ ], 508 (100) [M ⁺ - C ₁₃ H ₂₆ ], 374 (14), [M ⁺ - C ₂₁ H ₃₅ O ₂ ], 346 (19) [M ⁺ - C ₂₂ H ₃₄ NO ₂ ], 44 (15) [CH ₂ NO]. HRMS (C ₅₆ H ₅₅ N ₃ O ₇ ): Ber. m / z 690.309, Gef. m / z 690.308, Δ = 1 mmu. C ₅₆ H ₅₅ N ₃ O ₇ (882.1): Ber. C 76.25, H 6.09, N 4.76; Gef. C 75.88, H 6.38, N 4.59.

N- (1-Hexylheptyl) -N'-4- (5-phenyl-2-phenylisoxazolidin-3-yl) benzylperylene-3,4: 9,10-tetracarboxylic bisimide (5):

N- (1-Hexylheptyl) -N '- (4-N "-phenylcarbaldimine-N" -oxidobenzyl) perylene-3,4: 9,10-tetracarboxylic acid bisimide (4, 120 mg, 153 μmol) were dissolved in styrene ( 10 mL), heated to 85 ° C, cooled after 1 h, evaporated in vacuo and chromatographed (silica gel, CH ₂ Cl ₂ / MeOH 20: 1, mixture of two diastereomers, de = 77%). Y. 102 mg (75%), mp> 300 ° C. R _f (silica gel, CH ₂ Cl ₂ / MeOH 20: 1) = 0.79. IR (ATR): ν ~ = 3604.9 w, 3036.7 w, 2954.5 m, 2924.2 m, 2855.3 m, 1691.5 s, 1655.3 s, 1593.0 m, 1577.8 s, 1508.3 w, 1484.6 w, 1436.1 m, 1403.7 s, 1351.8 s, 1332.5 s, 1300.6 m, 1249.1 s, 1251.8 w, 1169.9 m, 1127.1 w, 1104.9 w, 1082.7 w, 1020.7 w, 983.9 w, 924.9 w, 854.54 w, 810.2 s, 796.1 w, 771.8 m, 748.3 s, 696.2 s cm ^-1 . Main diastereomer: ¹ H-NMR (600 MHz, CDCl ₃ , 25 ° C): δ = 0.82 (t, 3H, ³ J = 7.0 Hz, CH ₃ ), 1.19-1.38 (m, 16H, CH ₂ ), 1.85- 1.91 (m, 2H, β-CH ₂ ), 2.22-2.29 (m, 2H, β-CH ₂ ), 2.43 (ddd, 1H, ³ J = 7.9 Hz, ³ J = 10.3 Hz, ² J = 12.2 Hz, CH ₂ ), 3.14 (ddd, 1H, ³ J = 5.7 Hz, ³ J = 7.9 Hz, ² J = 12.2 Hz, CH ₂ ), 4.88 (t, 1H, ³ J = 7.9 Hz, CH), 5.14 (dd , 1H, ³ J = 5.7 Hz, ³ J = 10.3 Hz, CH), 5:16 to 5:21 (m, 1H, α-CH), 5:39 (d, 1H, N-CH _2), 5:42 (d, 1H, N -CH ₂ ), 6.88-6.91 (m, 1H, H _aryl ), 7.01 (d, 2H, ³ J = 1.0 Hz, H _aryl ), 7.02 (d, 2H, ³ J = 1.0 Hz, H _aryl ), 7.21 (d, 2H, ³ J = 7.4 Hz, H _aryl), 7.23 (d, 2H, ³ J = 7.4 Hz, H _aryl), 7:28 to 7:30 (m, 1H, H _aryl), 7:32 to 7:35 (m, 2H , H _aryl ), 7.39-7.41 (m, 2H, H _aryl ), 7.52 (d, 2H, ³ J = 8.4 Hz, H _aryl ), 7.61 (d, 2H, ³ J = 8.4 Hz, H _aryl ), 8.52 -8.65 ppm (m, 8H, H _perylene ). Additional diastereomer: ¹ H-NMR (600 MHz, CDCl ₃ , 25 ° C): δ = 0.82 (t, 3H, ³ J = 7.0 Hz, CH _3), 1:19 to 1:38 (m, 16H, CH _2), 1.85-1.91 (m, 2H, β-CH ₂₎ 2.22 -2.29 (m, 2H, β-CH ₂ ), 2.61 (ddd, 1H, ³ J = 4.5 Hz, ³ J = 6.5 Hz, ² J = 12.0 Hz, CH ₂ ), 2.74 (td, 1H, ³ J = 9.1 Hz, ² J = 12.0 Hz, CH ₂ ), 4.66 (dd, 1H, ³ J = 4.5 Hz, ³ J = 9.1 Hz, CH), 5.16-5.21 (m, 1H, α-CH), 5.31 (dd , 1H, ³ J = 6.5 Hz, ³ J = 9.1 Hz, CH), 5:39 (d, 1H, N-CH _2), 5:42 (d, 1H, N-CH _2), 6.88-6.91 (m, 1H, H _aryl ), 6.96 (d, 2H, ³ J = 1.0 Hz, H _aryl ), 6.97 (d, 2H, ³ J = 1.0 Hz, H _aryl ), 7.15 (d, 2H, ³ J = 7.4 Hz, H _aryl ), 7.17 (d, 2H, ³ J = 7.4 Hz, _aryl ), 7.28-7.30 (m, 1H, _aryl ), 7.32-7.35 (m, 2H, _aryl ), 7.39-7.41 (m, 2H, H _aryl), 7:52 (d, 2H, ³ J = 8.4 Hz, H _aryl), 7.61 (d, 2H, ³ J = 8.4 Hz, H _aryl), 8.52-8.65 ppm (m, 8H, H _perylene). ¹³ C-NMR (150 MHz, CDCl _3, 25 ° C): δ = 14.0, 22.6, 26.9, 29.2, 31.8, 32.4, 43.4, 47.2, 48.8, 54.8, 69.4, 71.4, 80.5, 113.9, 115.8, 122.9, 123.2, 126.5, 126.8, 128.5, 128.9, 129.6, 129.7, 131.0, 131.8, 134.2, 134.8, 136.2, 137.7, 142.4, 152.5, 163.4 ppm. UV / Vis (CHCl ₃ ): λ _max (ε) = 459 (18,800), 491 (52,100), 527 nm (85,700). HRMS (C ₅₉ H ₅₆ N ₃ O ₅ ): Ber. m / z: 886,426, Gef. m / z: 886,430, Δ = 4 mmu. C ₅₉ H ₅₅ N ₃ O ₅ · H ₂ O (885.4): Ber. C 78.38, H 6.35, N 4.65; Gef. C 78.17, H 6.70, N 4.34.

N- (1-hexylheptyl) -N-4- (5-cyano-2-phenylisoxazolidin-3-yl) benzylperylen-3,4: 9,10-tetracarbonsäurebisimid (8) and N- (1-hexylheptyl) -N'-4- (4-cyano-2-phenylisoxazolidin-3-yl) benzylperylene-3,4: 9,10-tetracarboxylic bisimide (9):

N- (1-Hexylheptyl) -N '- (4-N "-phenylcarbaldimine-N'-oxidobenzyl) perylene-3,4: 9,10-tetracarboxylic bisimide (4, 110 mg, 153 μmol) was dissolved in acrylonitrile (50 mL), boiled under reflux for 1 h, cooled, evaporated in vacuo and chromatographed (silica gel, CH ₂ Cl ₂ / MeOH 45: 1, mixture of two diastereomers, de = 52%). Y. 94 mg (73%). M.p.> 300 ° C. R _f (silica gel, CH ₂ Cl ₂ / MeOH 20: 1) = 0.79. Main diastereomer: ¹ H-NMR (600 MHz, CDCl ₃ , 25 ° C): δ = 0.82 (t, 3H, ³ J = 7.0 Hz, CH ₃ ), 1.19-1.38 (m, 16H, CH ₂ ), 1.85- 1.91 (m, 2H, β-CH ₂ ), 2.22-2.29 (m, 2H, β-CH ₂ ), 2.47 (ddd, 1H, ³ J = 3.9 Hz, ³ J = 5.9 Hz, ² J = 12.8 Hz, CH ₂ ), 3.15 (ddd, 1H, ³ J = 3.9 Hz, ³ J = 9.0 Hz, ² J = 12.8 Hz, CH ₂ ), 4.47 (dd, 1H, ³ J = 5.9 Hz, ³ J = 9.0 Hz, CH), 4.95 (dd, 1H, ³ J = 3.9 Hz, ³ J = 9.0 Hz, CH), 5:16 to 5:21 (m, 1H, α-CH), 5:41 (s, 2H, _N-CH2), 6.94 -6.95 (m, 3H, _aryl ), 7.18-7.24 (m, 2H, _aryl ), 7.49 (d, 2H, ³ J = 8.3 Hz, _aryl ), 7.61 (d, 2H, ³ J = 8.3 Hz , H _aryl ), 8.55-8.66 ppm (m, 8H, H _perylene ). Additional diastereomer: ¹ H-NMR (600 MHz, CDCl ₃ , 25 ° C): δ = 0.82 (t, 3H, ³ J = 7.0 Hz, CH ₃ ), 1.19-1.38 (m, 16H, CH ₂ ), 1.85- 1.91 (m, 2H, β-CH ₂ ), 2.22-2.29 (m, 2H, β-CH ₂ ), 2.77 (ddd, 1H, ³ J = 6.1 Hz, ³ J = 7.6 Hz, ² J = 12.5 Hz, CH ₂ ), 2.98 (ddd, 1H, ³ J = 5.2 Hz, ³ J = 7.6 Hz, ² J = 12.5 Hz, CH ₂ ), 4.87 (dd, 1H, ³ J = 5.2 Hz, ³ J = 7.6 Hz, CH), 4.95-4.97 (m, 1H, CH), 5:16 to 5:21 (m, 1H, α-CH), 5:41 (s, 2H, N-CH _2), 6.94-6.95 (m, 3H, H _aryl) , 7.18-7.24 (m, 2H, _aryl ), 7.49 (d, 2H, ³ J = 8.3 Hz, _aryl ), 7.61 (d, 2H, ³ J = 8.3 Hz, _aryl ), 8.55-8.66 ppm ( m, 8H, H _perylene ). C ₅₄ H ₅₀ N ₄ O ₅ (834.4): Ber. C 77.67, H 6.04, N 6.71; Gef. C 77.30, H 5.89, N 6.31.

N- (1-hexylheptyl) -N'-4- (4-methyloxycarbonyl-5-methyl-2-phenylisoxazolidin-3-yl) benzylperylen-3,4: 9,10-tetracarbonsäurebisimid (7):

N- (1-Hexylheptyl) -N- (4-N "-phenylcarbaldimine-N" -oxidobenzyl) perylene-3,4: 9,10-tetracarboxylic bisimide (4.125 mg, 0.15 mmol) was added to methyl crotonic acid (20 mL), heated to 65 ° C. for 6 h (reflux), evaporated in vacuo, chromatographed (silica gel, dichloromethane / methanol 50: 1, non-fluorescent band), dissolved in a little chloroform and precipitated with methanol. Y. 80 mg (62.6%), bright red solid, mp> 300 ° C. R _f (silica gel, dichloromethane / methanol 30: 1) = 0.82. IR (ATR): ν ~ = 2935.4 w, 2923.6 m, 2853.9 m, 1736.0 w, 1693.4 s, 1654 s, 1592.7 s, 1577.5 m, 1507.3 w, 1486.1 w, 1434.1 m, 1403.2 m, 1376.9 w, 1331.6 s, 1247.3 m, 1216.2 w, 1169.3 w, 1124.5 w, 1105.0 w, 1020.8 w, 987.5 w, 851.8 w, 808.8 m, 744.0 m, 694.4 w cm ^-1 . ¹ H-NMR (600 MHz, CDCl ₃ , 25 ° C): δ = 0.82 (t, ³ J (H, H) = 7.0 Hz, 6H, 2 x CH ₃ ), 1.23-1.30 (m, 16H, 8 × CH ₂ ), 1.46 (d, ³ J (H, H) = 5.9 Hz, 3H, CH ₃ ), 1.81-1.88 (m, 2H, β-CH ₂ ), 2.21-2.27 (m, 2H, β- CH ₂ ), 3.12 (dd, ³ J (H, H) = 7.1 Hz, ³ J (H, H) = 9.2 Hz, 1H, CH), 4.38 (qd, ³ J (H, H) = 5.9 Hz, ³ J (H, H) = 9.2 Hz, 1H, CH), 5.10 (d, ³ J (H, H) = 7.1 Hz, 1H, CH), 5.15-5.22 (m, 1H, α-CH ₂ ), 7.19-7.22 (m, 5H, CH _Aromat ), 7.53 (dd, ³ J (H, H) = 6.2 Hz, 4H, CH _Aromat ), 8.63-8.73 ppm (m, 8H, CH _perylene ). ¹³ C-NMR (151 MHz, CDCl _3, 25 ° C): δ = 14.3, 22.8, 27.1, 29.4, 29.9, 32.0, 32.6, 55.0, 122.4, 123.8, 126.7, 129.1, 129.8, 131.9, 135.2, 136.7, 163.7 ppm. UV / Vis (CHCl _3): λ _max (ε) = 459 (21500), 490 (52400), 527 nm (84700). HRMS (C ₅₆ H ₅₆ N ₃ O ₅ ): Ber. m / z: 882,408; Gef. M / z: 882.409. Δ = 1 mmu. C ₅₆ H ₅₅ N ₃ O ₅ (882.1): Ber. C 76.25, H 6.28, N 4.76; Gef. C 75.84, H 6.16, N 4.58.

N- (1-hexylheptyl) -N-4- (5-phenyl-2-phenylisoxazolidin-3-yl) biphenylmethyl-perylene-3,4: 9,10-tetracarbonsäurebisimid (12):

N- (1-Hexylheptyl) -N- (4-N "-methylcarbaldimine-N'-oxidobiphenyl) perylene-3,4: 9,10-tetracarboxylic bisimide (10, 100 mg, 0.130 mmol) was dissolved in 5 mL of styrene and N-phenylhydroxylamine (142 mg, 1.30 mmol), stirred for 25 h at 85 ° C, stirred for 40 h at room temperature, evaporated in vacuo, dissolved in dichloromethane, applied to a chromatography column, chromatographed (silica gel, dichloromethane / methanol 70: 1, first non-fluorescent band), precipitated from a little dichloromethane with methanol, filtered off and dried at 110 ° C. (two diastereomers, de = 28%). Y. 34 mg (27%) of a red solid, mp> 300 ° C. R _f (Silica gel, chloroform / ethanol = 60: 1) = 0.28. IR (ATR): ν ~ = 3066.9 w, 2952.0 m, 2923.4 m, 2854.1 m, 1691.8 s, 1646.1 s, 1592.0 s, 1575.4 m, 1483.0 w, 1457.9 w, 1435.6 w, 1402.6 m, 1334.8 s, 1249.0 m, 1170.8 m, 1125.9 w, 1108.1 w, 1069.6 w, 1022.9 w, 987.3 w, 892.3 w, 850.5 w, 832.3 w, 809.6 m, 763.0 w, 684.9 w, 660.6 w, 622.5 w cm ^-1 . Main diastereomer: ¹ H-NMR (600 Hz, CDCl ₃ , 25 ° C): δ = 0.82 (t, ³ J _{H, H} = 7.0 Hz, 6H, CH ₃ ), 1.21-1.36 (m, 16H, CH ₂ ) , 1.84-1.90 (m, 2H, β-CH ₂ ), 2.20-2.28 (m, 2H, β-CH ₂ ), 2.50 (ddd, ³ J _{H, H} = 7.7 Hz, ³ J _{H, H} = 10.2 Hz , ² J _{H, H} = 12.2 Hz, 1H, CH ₂ ), 3.20 (ddd, ³ J _{H, H} 5.8 Hz, ³ J _{H, H} = 8.0 Hz, ² J _{H, H} = 12.2 Hz, 1H, CH ₂ ), 4.95 (dd, ³ J _{H, H} = 7.8 Hz, 1H, CH), 5:16 to 5:21 (m, 2H, α-CH, CH), 5:46 (s, 2H, CH ₂ -N), 6.93-7.72 (m, 18H, H _arom ), 8.63-8.73 ppm (m, 8H, H _perylene ). Sub-diastereomer (36%): 1 H-NMR (600 Hz, CDCl ₃ , 25 ° C): δ = 0.82 (t, ³ J _{H, H} = 7.0 Hz, 6H, CH ₃ ), 1.21-1.36 (m, 16, CH ₂ ), 1.84-1.90 (m, 2, β-CH ₂ ), 2.20-2.28 (m, 2, β-CH ₂ ), 2.69 (ddd, ³ J _{H, H} = 4.6 Hz, ³ J _{H, H} = 6.6 Hz, ² J _{H, H} = 12.0, 1H, CH), 2.78-2.83 (m, 1H, CH), 4.72 (dd, ³ J _{H, H} = 4.6 Hz, ³ J _{H, H} = 6.6 Hz, 1H, CH), 5.16-5.21 (m, 1H, α-CH), 5.34-5.39 (m, 1H, CH), 5.46 (s, 2H, CH ₂ -N), 6.93-7.72 (m, 18H, H _arom ), 8.63-8.73 ppm (m, 8H, H _perylene ). ¹³ C-NMR (150 MHz, CDCl _3, 25 ° C): δ = 14.0, 22.6, 26.9, 29.2, 29.7, 31.8, 32.4, 43.5, 48.7, 54.8, 71.5, 80.8, 114.0, 121.4, 123.0, 126.7, 126.9, 127.2, 127.5, 128.6, 129.0, 129.5, 131.8, 135.0, 136.1, 137.8, 139.9, 140.2, 142.0, 152.5, 163.5 ppm. UV / Vis (CHCl ₃ ): λ _max (E _rel ) = 459 (0.21), 490 (0.60), 527 nm (1.0). HRMS (C ₆₅ H ₆₀ N ₃ O _5): Calcd. m / z: 962,456; Gef. M / z: 962.459, Δ = 3 mmu.

4- (1,3-dioxolan-2-yl) -4-methylbenzonitrile [13]:

4-Cyanoacetophenone (5.0 g, 34.4 mmol) was dissolved in toluene (50 mL), treated dropwise with ethylene glycol (3.4 g, 55.1 mmol) and BF ₃ etherate (0.5 mL), heated under reflux on a water for 12 h, to room temperature Allow to cool (yellow reaction solution), with 5 percent. Sodium bicarbonate solution (40 mL), extracted with diethyl ether, washed with saturated sodium chloride solution (30 mL), dried over MgSO ₄ , filtered, evaporated in vacuo and recrystallized from diethyl ether / n-pentane (1: 1). Y. 2.2 g (34%) of colorless solid, mp 70 ° C. ¹ H-NMR (200 MHz, CDCl _3, 25 ° C): δ = 1.62 (s, 3 H, CH _3), 3.72-3.75 (m, 2H, CH _2), 4:02 to 4:08 (m, 2H, CH ₂ ), 7.57-7.64 ppm (m, 4H, H _aryl ). HRMS (C ₁₁ H ₁₂ NO ₂ ): Ber. m / z: 190,086, Gef. m / z: 190,087, d = 1 mmu.

4- (1,3-dioxolan-2-yl) -4-methylbenzylamine [13]:

Under argon at 0 ° C to a suspension of lithium aluminum hydride (800 mg, 21.1 mmol) in diethyl ether (20 mL) over 15 minutes 4- (1,3-dioxolan-2-yl) -4-methylbenzonitrile (2.00 g, 10.6 mmol) in diethyl ether (10 mL) was carefully added dropwise, stirred for 2 h at 0 ° C, stirred for 16 h at room temperature, carefully mixed with aqueous NaOH solution (2 N, 20 mL) dropwise, extracted with ether (3 × 50 mL) , dried over MgSO ₄ , filtered and evaporated in vacuo. Y. 1.32 g (64%) colorless liquid, n 20 / D = 1.552. ¹ H-NMR (200 MHz, CDCl _3, 25 ° C): δ = 1.63 (s, 3H, CH _3), 3.72-3.75 (m, 2H, CH _2), 3.84 (s, 2H, N-CH ₂ ) 4.02-4.08 (m, 2H, CH ₂ ), 7.26 (d, 2H, ³ J = 8.3 Hz, H _aryl ) 7.43 ppm (d, 2H, ³ J = 8.3 Hz, H _aryl ). MS (DEI ⁺ / 70 eV): m / z (%): 193 (5) [M ⁺ ], 178 (100), 134 (39), 87 (20), 43 (11).

N- [4- (2-Methyl [1,3] dioxolan-2-yl) benzyl] -N '- (1-hexylheptyl) perylene-3,4: 9,10-tetracarbonsäurebisimid:

N-1-hexylheptylperylene-1,3: 9,10-tretracarboxylic acid-3,4-anhydride-9,10-carboxylic acid imide (270 mg, 0.47 mmol) was initially charged in imidazole (5 g), heated to 140 ° C, with Added 4- (1,3-dioxolan-2-yl) -4-methylbenzylamine (110 mg, 0.56 mmol), stirred at 140 ° C for 3 h, while still warm with a few milliliters of ethanol and 2 N hydrochloric acid (50 mL) , filtered off after complete cooling, washed with aqueous 2 N HCl, dried for 16 h in a drying oven at 110 ° C, dissolved in a little chloroform and chromatographed (silica gel CHCl ₃ / EtOH 30: 1). Y. 246 mg (70%) of red dye, mp> 300 ° C. R _f (silica gel, chloroform / ethanol 30: 1) = 0.17. IR (ATR): ν ~ = 2955.0 m, 2923.9 m, 2856.0 m, 1693.1 m, 1648.4 s, 1592.9 m, 1576.5 m, 1507.5 w, 1482.9 w, 1456.8 w, 1435.9 m, 1420.5 w, 1403.7 m, 1378.5 w, 1339.3 m, 1284.2 m, 1249.1 m, 1173.2 m, 1135.5 w, 1127.9 w, 1111.1 w, 1091.7 w, 1038.2 m, 1020.2 w, 983.8 w, 948.3 w, 862.4 w, 808.9 m, 781.1 w, 744.4 m, 725.4 w cm ^-1 . ¹ H-NMR (600 MHz, CDCl _3, 25 ° C): δ = 8:43 to 8:57 (m, 8H, H _Pery), 7:54 (d, 1H, ³ J = 8.5 Hz), 7:44 (d, 1H, ³ J = 8.5 Hz), 5.37 (s, 2H, CH ₂ -N), 5.16-5.21 (m, 1H, CH-N), 3.72-3.76 (m, 2H, CH ₂ ), 3.98-4.00 (m, 2H , CH ₂ ), 2.23-2.29 (m, 2H, β-CH ₂ ), 1.86-1.92 (m, 2H, β-CH ₂ ), 1.21-1.38 (m, 16H, CH ₂ ), 0.82 ppm (t, 1H, ³ J = 7.0 Hz). ¹³ C-NMR (150 MHz, CDCl _3, 25 ° C): δ = 163.2, 142.7, 136.6, 134.7, 131.7, 131.6, 129.4, 129.3, 129.1, 129.0, 128.6, 125.5, 123.1, 22.9, 122.9, 108.7, 64.4, 54.8, 43.4, 32.4, 31.8, 29.2, 27.6, 27.0, 22.6, 14.0 ppm. UV / Vis (CHCl _3): λ _max (ε) = 463 (81220), 492 (50320), 529 nm (18510). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 539 (1.00), 582 nm (0.40). Fluorescence quantum yield (CHCl ₃ , λ _exc = 491 nm, E _{491 nm} = 0.0347 cm ^-1 , reference: 1a with Φ = 1.00): 1.00. MS (DEI ⁺ / 70 eV): m / z (%) = 749 (21) [M ⁺ + H], 748 [M ⁺ ] (38), 735 (13), 734 (47), 733 (100) , 569 (12), 568 (18), 567 (21), 554 (11), 553 (34), 552 (41), 551 (43), 549 (13), 548 (31), 373 (11) , 276 (12), 275 (30). C ₄₈ H ₄₈ N ₂ O ₆ (748.9): Calcd. C 76.98, H 6.46, N 3.74; Gef. C 77.05, H 6.41, N 3.58.

N- (4-acetylbenzyl) -N '- (1-hexylheptyl) perylene-3,4: 9,10-tetracarbonsäurebisimid:

• [1] [a] L. Flamigni, B. Ventura, M. Tasior, T. Becherer, H. Langhals, D. T. Gryko, Chem. Eur. J. 2008, 14, 169–183 . [b] M. Tasior, D. T. Gryko, Jing Shen, K. M. Kadish, T. Becherer, H. Langhals, B. Ventura, L. Flamigni, J. Phys. Chem. C 2008, publiziert online 17. November 2008, JP8065635 .
• [2] [a] H. Langhals, Helv. Chim. Acta. 2005, 88, 1309–1343. [b] H. Langhals, Heterocycles 1995, 40, 477–500 . [c] H. Langhals, Molecular Devices. Chiral, Bichromophoric Silicones: Ordering Principles in Complex Molecules in F. Ganachaud, S. Boileau, B. Boury (eds.), Silicon Based Polymers, p. 51–63, Springer, 2008, ISBN 978-1-4020-8527-7, e-ISBN 978-1-4020-8528-4 .
• [3] H. Langhals, J. Karolin, L. B.-Å. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919–2922 .
• [4] H. Langhals, S. Demmig, H. Huber, Spectrochim. Acta 1988, 44A, 1189–1193 .
• [5] [a] S. Demmig, H. Langhals, Chem. Ber. 1988, 121, 225–230. [b] H. Langhals, S. Demmig, T. Potrawa, J. Prakt. Chem. 1991, 333, 733–748 .
• [6] H. Langhals, W. Jona, Chem. Eur. J. 1998, 4, 2110–2116 .
• [7] H. Langhals, A. Obermeier, Eur. J. Org. Chem. 2008, im Druck .
• [8] [a] P. Grünanger, P. Vita-Finzi, Isoxazolidines, in The Chemistry of Heterocyclic compounds (E. C. Tayloer, A. Weissberger, Editoren) Vol. 49/1, S. 649–877, Wiley, New York 1991, ISBN 0-471-02233-0 . [b] S. Cicchi, F. M. Cordero, D. Giomi, Five-membered ring systems: with O & N atoms in Progress in Heterocyclic Chemistry 2003, 15, 261–283 . [c] Y. Takeuchi, F. Furusaki, The chemistry of isoxazolidines in Advances in Heterocyclic Chemistry 1977, 21, 207–251 .
• [9] H. Langhals, T. Becherer, J. Lindner, A. Obermeier, Eur. J. Org. Chem. 2007, 4328–4336 .
• [10] [a] R. Huisgen, R. Grashey, H. Hauck, H. Seidl, Chem. Ber. 1968, 101 (7), 2548–2558 . [b] R. Grashey, R. Huisgen, H. Leitermann, Tetrahedron Lett. 1960, 12, 9–13 . [c] C. W. Brown, K. Marsden, M. T. A. Rogers, C. M. B. Taylor, R. Wright, Proc. Chem. Soc. 1960, 254–255 . [d] G. R. Delpierre, M. Lamchen, Proc. Chem. Soc. 1960, 386–387 .
• [11] R. Huisgen, R. Grashey, H. Hauck, H. Seidl, Chem. Ber. 1968, 101, 2568–2584 .
• [12] K. Rueck-Braun, T. E. H. Freysoldt, F. Wierschem, Chem. Soc. Revs. 2005, 34, 507–516 .
• [13] W. Korytnyk, N. Angelino, C. Dave, L. Caballas, J. Med. Chem. 1978, 21, 507–513 .

For acetal cleavage, N- [4- (2-methyl [1,3] dioxolan-2-yl) benzyl] -N '- (1-hexylheptyl) perylene-3,4: 9,10-tetracarboxylic bisimide (1.72 g, 2.30 mmol) in tetrahydrofuran (220 mL) at 70 ° C, treated with aqueous 2 N hydrochloric acid (50 mL), heated to 70 ° C for 5 h, precipitated by addition of 2 N hydrochloric acid, filtered off, washed and at 110 ° C dried. Y. 1.60 g (98%) of red dye, mp> 300 ° C. R _f (silica gel, chloroform / ethanol 30: 1) = 0.83. IR (ATR): ν ~ = 2957.0 m, 2922.1 m, 2855.1 m, 1696.8 m, 1674.8 m, 1647.9 s, 1608.3 w, 1592.9 m, 1576.1 m, 1507.7 w, 1482.9 w, 1466.3 w, 1436.6 m, 1403.7 m, 1379.4 w, 1336.4 s, 1310.1 m, 1251.0 m, 1192.4 w, 1171.6 m, 1124.9 w, 1114.6 w, 1076.7 w, 1019.5 w, 988.5 m, 956.4 w, 852.2 w, 839.8 m, 808.9 s, 796.4 m, 783.5 m , 745.6 s, 727.9 w, 683.9 w cm ^-1 . ¹ H-NMR (600 Hz, CDCl _3, 25 ° C): δ = 0.82 (t, 6H, ³ J _{H, H} = 7.1 Hz, CH _3), 1:19 to 1:39 (m, 16H, CH _2), 1.85 -1.91 (m, 2H, β-CH ₂ ), 2.22-2.28 (m, 2H, β-CH ₂ ), 5.18 (tt, ³ J _{H, H} = 5.8 Hz, ³ J _{H, H} = 9.3 Hz, 1H , α-CH), (5:44 s, 2H, CH ₂ -N), 7.77 (d, ³ J _{H, H} = 8.5 Hz, ⁴ J _{H, H} = 173.9 Hz, 4H, H _arom), 8.55-8.65 ppm (m, 8H, H _perylene ). ¹³ C-NMR (150 MHz, CDCl _3, 25 ° C): δ = 14.0, 22.6, 26.6, 27.0, 29.2, 29.7, 31.8, 32.4, 43.5, 54.9, 122.8, 123.0, 123.3, 126.3, 126.5, 128.6, 129.0, 129.5, 131.7, 134.1, 135.0, 136.4, 142.7, 163.3 ppm. UV / Vis (CHCl _3): λ _max (ε) = 462 (20570), 491 (51780), 527 nm (84530). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 539 (1.00), 582 nm (0.40). Fluorescence quantum yield (CHCl ₃ , λ _exc = 491 nm, E _{491 nm} = 0.0294 cm ^-1 , reference: 1a with Φ = 1.00): 1.00. MS (DEI ⁺ / 70 eV): m / z (%) = 705 [M ⁺ + H] (24), 704 [M ⁺ ] (37), 524 (24), 523 (76), 522 (100) , 508 (11), 507 (24), 390 [M ⁺ -C ₁₃ H ₂₇ -C ₉ H ₉ O] (7), 374 (15), 373 (9), 346 (12), 254 (11) , 55 (8). HRMS (C ₄₆ H ₄₄ N ₂ O ₅ ): Ber. m / z: 704,327, Gef. m / z: 704,330, Δ = 3 mmu. C ₄₆ H ₄₄ N ₂ O ₅ (704.3): Ber. C 78.38, H 6.29, N 3.97; Gef. C 77.96, H 6.21, N 3.91.

• [1] [a] Flamigni, B. Ventura, M. Tasior, T. Becherer, H. Langhals, DT Gryko, Chem. Eur. J. 2008, 14, 169-183 , [b] M. Tasior, DT Gryko, Jing Shen, KM Kadish, T. Becherer, H. Langhals, B. Ventura, L. Flamigni, J. Phys. Chem. C 2008, published online November 17, 2008, JP8065635 ,
• [2] [a] H. Langhals, Helv. Chim. Acta. 2005, 88, 1309-1343. [b] H. Langhals, Heterocycles 1995, 40, 477-500 , [C] H. Langhals, Molecular Devices. Chiral, Bichromophoric Silicones: Ordering Principles in Complex Molecules in F. Ganachaud, S. Boileau, B. Boury (eds.), Silicon Based Polymers, p. 51-63, Springer, 2008, ISBN 978-1-4020-8527-7, e-ISBN 978-1-4020-8528-4 ,
• [3] H. Langhals, J. Karolin, LB-Å. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919-2922 ,
• [4] H. Langhals, S. Demmig, H. Huber, Spectrochim. Acta 1988, 44A, 1189-1193 ,
• [5] [a] S. Demmig, H. Langhals, Chem. Ber. 1988, 121, 225-230. [b] H. Langhals, S. Demmig, T. Potrawa, J. Prakt. Chem. 1991, 333, 733-748 ,
• [6] H. Langhals, W. Jonah, Chem. Eur. J. 1998, 4, 2110-2116 ,
• [7] H. Langhals, A. Obermeier, Eur. J. Org. Chem. 2008, in press ,
• [8] [a] P. Grünanger, P. Vita-Finzi, Isoxazolidines, in The Chemistry of Heterocyclic Compounds (EC Tayloer, A. Weissberger, editors) Vol. 49/1, pp. 649-877, Wiley, New York 1991, ISBN 0-471 -02233-0 , [B] S. Cicchi, FM Cordero, D. Giomi, Five-membered ring systems: with O & N atoms in progress in Heterocyclic Chemistry 2003, 15, 261-283 , [C] Y. Takeuchi, F. Furusaki, The chemistry of isoxazolidines in Advances in Heterocyclic Chemistry 1977, 21, 207-251 ,
• [9] H. Langhals, T. Becherer, J. Lindner, A. Obermeier, Eur. J. Org. Chem. 2007, 4328-4336 ,
• [10] [a] R. Huisgen, R. Grashey, H. Hauck, H. Seidl, Chem. Ber. 1968, 101 (7), 2548-2558 , [B] R. Grashey, R. Huisgen, H. Leitermann, Tetrahedron Lett. 1960, 12, 9-13 , [C] CW Brown, K. Marsden, MTA Rogers, CMB Taylor, R. Wright, Proc. Chem. Soc. 1960, 254-255 , [D] GR Delpierre, M. Lamchen, Proc. Chem. Soc. 1960, 386-387 ,
• [11] R. Huisgen, R. Grashey, H. Hauck, H. Seidl, Chem. Ber. 1968, 101, 2568-2584 ,
• [12] K. Rueck-Braun, TEH Freysoldt, F. Wierschem, Chem. Soc. Revs. 2005, 34, 507-516 ,
• [13] Korytnyk, N. Angelino, C. Dave, L. Caballas, J. Med. Chem. 1978, 21, 507-513 ,

Subject of the invention

• 1. Use of α-effect compounds of general formula 13 as electron donor groups in light-driven systems for charge separation,
  
  in which x and y may be identical or different and denote elements having free, nonbonding electron pairs, preferably elements of the second and third period, such as nitrogen, oxygen, fluorine, Sulfur and chlorine, preferably the second period elements and most preferably nitrogen and oxygen, and wherein R ¹ to R ^{3 may be the} same or different and independently represent hydrogen or linear alkyl radicals having at least one and at most 37 represent C atoms in which one to 10 CH ₂ units can be replaced independently of one another by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CH = CH groups, in which a CH unit is also may 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 ⁹ may also independently of one another denote the halogen atoms F, Cl, Br or I.
• 2. Use of isoxazolidines of general formula 14 as electron donor groups in light-driven systems for charge separation,
  
  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 be independently replaced on the same carbon atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group or a li neare alkyl chain having up to 18 carbon atoms, in which one to 6 CH ₂ units may be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium, cis- or trans-CH = CH groups in which a CH May also be replaced by a nitrogen atom, acetylenic C≡C groups, 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2 , 6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1, 4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms have been replaced by nitrogen atoms may, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3 -, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which one to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit can also be replaced by a nitrogen atom, acetylenic C ≡C groups 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9-, 2,10- or r 9,10-Disubstituierte Anthracenreste in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or the quaternary carbon atoms can be linked in pairs, so that rings are formed, such. B. cyclohexane rings. The radicals R ¹ to R ⁹ may also independently of one another denote the halogen atoms F, Cl, Br or I.
• 3. perylenebisimide dyads of general formula 15,
  
  in which the radicals R ¹ to R ^{10 may be the} same 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 in each case carbonyl groups , Oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡C groups 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2 , 5- or 3,4-disubstituted thiophene 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 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 six CH ₂ units can be replaced independently by carbonyl groups, oxygenato me, 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-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 ¹ to R ⁹ may also independently of one another denote the halogen atoms F, Cl, Br or I. X in 15 may represent one to 12 CH ₂ units in which one or more may be independently replaced by each of 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, 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 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.
• 4. Perylenetetracarboxylic bisimide-nitrones of general formula 16,
  
  in which the radicals R ¹ to R ⁵ and X have the meaning given under 3.
• 5. A method characterized in that the Perylenbisimid dyads after 3 by 1,3-dipolar cycloaddition of nitrones according to 4 and Olefins are synthesized.
• 6. Process characterized in that the perylenebisimide-nitrones according to 4 from Perylenbisimid-Alde hy- droxylamine derivatives are synthesized, preferred hydroxylamine derivatives are N-methylhydroxylamine and N-phenylhydroxylamine.
• 7. Use of the substances according to 1 to 3 for the production of Solar energy, preferably in photovoltaic cells.
• 8. Use of the substances according to 1 to 3 for chemical Reactions by using them as light-driven reducing agents become.
• 9. Use of the substances according to 1 and 3 for chemical Reactions by being used as light-driven oxidants become.
• 10. Use of the substances according to 3 as fluorescence indicators for protonic acids, preferably minrealic acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.
• 11. Use of the substances according to 3 as fluorescence indicator for Lewis acids, zinc chloride, water-free one (II) chloride, anhydrous iron (III) chloride, anhydrous Aluniniumchlorid.
• 12. Use of the substances according to 1 to 3 in titanium dioxide solar cells, such as B. the Grätzel cell.
• 13. Use of the substances according to 4 as an indicator of Olefins via their 1,3-dipolar cycloaddition. preferred Olefins are unsaturated fatty acids if you want oleic acid, Linoleic acid and linolenic acid or else their trans isomers, which are known as trans fatty acids and distinction of cis-fatty acids of trans-fatty acids.
• 14. Use of the substances according to 3 and 4 as pigments for Paints and related colors such as watercolor paints and watercolors and colors for inkjet printers paper inks, printing inks, Inks and inks and other colors for painting and writing purposes and in paints.
• 15. Use of the substances according to 3 and 4 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).
• 16. Use of the dyes according to 3 and 4 in data memories, preferably in optical memories. Examples are systems like the CD or DVD discs.
• 17. Use of the substances according to 3 and 4 as fluorescent dyes.
• 18. Use of the substances according to 3 and 4 in OLEDS (organic LEDs).
• 19. Use of the substances according to 3 and 4 in photovoltaic Attachments.
• 20. Application of the dyes of 3 and 4 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.
• 21. Application of the dyes of 3 and 4 for staining of natural substances. Examples are paper, wood, straw, or natural Fiber materials such as cotton, jute, sisal, hemp, flax, hair and animal hair, wool or their transformation products such. B. the Viscose fiber, nitrate silk or copper rayon (rayon).
• 22. Application of the dyes of 3 and 4 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.
• 23. Application of the dyes of 3 and 4 as colorants, z. B. for coloring paints, varnishes and other paints, Paper colors, printing inks, inks and other colors for Painting and writing purposes.
• 24. Application of the dyes of 3 and 4 as pigments in the Electrophotography: z. B. for dry copying systems (Xerox process) and laser printers (non-impact printing).
• 25. Use of the dyes of 3 and 4 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.
• 26. Application of the dyes of 3 and 4 as an additive to others Colors where a certain shade of color is to be achieved particularly bright shades are preferred.
• 27. Use of the dyes of 3 and 4 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.
• 28. Application of the dyes of 3 and 4 as fluorescent dyes for machine-readable markers, alphanumeric are preferred Imprints or barcodes.
• 29. Application of the dyes of 3 and 4 for frequency conversion from light, z. B. from short-wave light of longer wavelength, to make visible light.
• 30. Application of Dyes of 3 and 4 in Display Elements for Numerous Display, Note and Mar coding purposes, eg B. passive display elements, information and traffic signs, such as traffic lights.
• 31. Application of Dyes of 3 and 4 in Inkjet Printers in homogeneous solution as a fluorescent ink.
• 32. Application of the dyes of 3 and 4 as starting material for superconducting organic materials.
• 33. Use of Dyes of 3 and 4 for solid fluorescence labels.
• 34. Use of the dyes of 3 and 4 for decorative Purposes.
• 35. Application of the dyes of 3 and 4 for artistic Purposes.
• 36. application of the dyes of 3 and 4 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).
• 37. Application of the dyes of 3 and 4 as fluorescent dyes in highly sensitive detection methods.
• 38. Application of the dyes of 3 and 4 as fluorescent dyes in scintillators.
• 39. Application of the dyes of 3 and 4 as dyes or Fluorescent dyes in optical light harvesting systems.
• 40. Application of the dyes of 3 and 4 as dyes or Fluorescent dyes in fluorescence solar collectors.
• 41. Application of the dyes of 1 in liquid crystals for redirecting light.
• 42. Application of the dyes of 3 and 4 as dyes or Fluorescent dyes in fluorescence-activated displays.
• 43. Application of the dyes of 3 and 4 as dyes or Fluorescent dyes in cold light sources for light-induced polymerization for the representation of plastics.
• 44. Application of the dyes of 3 and 4 as dyes or Fluorescent dyes for material testing, eg. B. in the Production of semiconductor circuits.
• 45. Application of the dyes of 3 and 4 as dyes or Fluorescent dyes for the study of integrated microstructures Semiconductor devices.
• 46. Application of the dyes of 3 and 4 as dyes or Fluorescent dyes in photoconductors.
• 47. Application of the dyes of 3 and 4 as dyes or Fluorescent dyes in photographic processes.
• 48. Application of the dyes of 3 and 4 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.
• 49. Application of the dyes of 3 and 4 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.
• 50. Application of the dyes of 3 and 4 as dyes or Fluorescent dyes in chemiluminescence systems, eg. In chemiluminescent light sticks, in luminescence immunoassays or other luminescence detection methods.
• 51. Application of the dyes of 3 and 4 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.
• 52. Application of the dyes of 3 and 4 as dyes or Fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams.
• 53. Application of the Dyes of 3 and 4 as Dyes in Dye Lasers as a Q-switch switch.
• 54. Application of the dyes of 3 and 4 as active substances for a nonlinear optics, e.g. B. for frequency doubling and the frequency tripling of laser light.
• 55. Application of the Dyes of 3 and 4 as Rheology Improver.
• 56. Application of Dyes of 3 and 4 for Leak Testing closed systems.

LIST OF REFERENCE NUMBERS

1 , Synthesis of nitrones 3 and 4 and reaction of 4 with styrene to give oxazolidines 5a and 5b.

2 , Synthesis of oxazolidines 6 to 8.

3 , Synthesis of nitrone 11 and oxazolidines 12a and 12b.

4 , Ground states and electronically excited states of 5 and 12.

5 , UV / Vis absorption and fluorescence spectra. The Osoxazolidine (above 400 nm congruent) compared with 1a (R = 1-hexylheptyl), which appears shorter wave by about half a nanometer. At 300 nm from top to bottom: 12, 1a, 5, 6 and 7.

QUOTES INCLUDE IN THE DESCRIPTION

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

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• H. Langhals, J. Karolin, LB-Å. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919-2922 [0027]
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• P. Granger, P. Vita-Finzi, Isoxazolidines, in The Chemistry of Heterocyclic Compounds (EC Tayloer, A. Weissberger, editors) Vol. 49/1, pp. 649-877, Wiley, New York 1991, ISBN 0- 471-02233-0 [0027]
• - S. Cicchi, FM Cordero, D. Giomi, Five-membered ring systems: with O & N atoms in progress in Heterocyclic Chemistry 2003, 15, 261-283 [0027]
• Y. Takeuchi, F. Furusaki, The chemistry of isoxazolidines in Advances in Heterocyclic Chemistry 1977, 21, 207-251 [0027]
• H. Langhals, T. Becherer, J. Lindner, A. Obermeier, Eur. J. Org. Chem. 2007, 4328-4336 [0027]
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Claims (56)

Use of α-effect compounds of general formula 13 as electron donor groups in light-driven systems for charge separation,

wherein x and y may be the same or different and denote elements having free, non-bonding electron pairs, preferably elements of the second and third periods, such as nitrogen, oxygen, fluorine, sulfur and chlorine, preferably the elements of the second period and most of these preferably nitrogen and oxygen, and in which in which the radicals R ¹ to R ^{3 may be the} same or different and independently of one another denote hydrogen or linear alkyl radicals having at least one and at most 37 C atoms, in which one to 10 CH ₂ units can be replaced independently by in each case carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, plate 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-disub substituted 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 ⁹ may also independently of one another denote the halogen atoms F, Cl, Br or I. 2. Use of isoxazolidines of general formula 14 as electron donor groups in light-driven systems for charge separation,

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 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 ⁹ may also independently of one another denote the halogen atoms F, Cl, Br or I. Perylenebisimide dyads of general formula 15,

in which the radicals R ¹ to R ^{10 may be the} same 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 in each case carbonyl groups , Oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡C groups 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2 , 5- or 3,4-disubstituted thiophene 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 be replaced independently of 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 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 also by a Nitrogen atom may be replaced, 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-disubstituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which one to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit can also be replaced by a nitrogen atom, acetylenic C ≡C groups 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9-, 2,10- or r 9,10-Disubstituierte Anthracenreste in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or the quaternary carbon atoms can be linked in pairs, so that rings are formed, such. B. cyclohexane rings. The radicals R ¹ to R ⁹ may also independently of one another denote the halogen atoms F, Cl, Br or I. X in 15 may represent one to 12 CH ₂ units in which one or more may be independently replaced by each of 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, 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 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. Perylenetetracarboxylic acid bisimide-nitrones of general formula 16,

in which the radicals R ¹ to R ⁵ and X have the meaning given under 3. Process characterized in that the Perylenbisimid dyads after 3 by 1,3-dipolar cycloaddition of nitrones according to 4 and Olefins are synthesized. Process characterized in that the perylenebisimide-nitrones 4 synthesized from perylenebisimide-aldehydes and hydroxylamine derivatives preferred hydroxylamine derivatives are N-methylhydroxylamine us N-phenylhydroxylamine .. Use of the substances according to 1 to 3 for the production of solar energy, preferably in photovoltaic cells. Use of the substances according to 1 to 3 for chemical reactions by acting as light-driven reducing agents be used. Use of the substances according to 1 and 3 for chemical reactions by acting as light-driven oxidants be used. Use of the substances according to 3 as fluorescence indicators for protonic acids, preferably minrealic acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid. Use of the substances according to 3 as fluorescence indicator for Lewis acids, zinc chloride, water-free one (II) chloride, anhydrous iron (III) chloride, anhydrous Aluniniumchlorid. Use of the substances according to 1 to 3 in titanium dioxide solar cells, such as B. the Grätzel cell. Use of the substances according to 4 as an indicator of Olefins via their 1,3-dipolar cycloaddition. preferred Olefins are unsaturated fatty acids if you want oleic acid, Linoleic acid and linolenic acid or else their trans isomers, which are known as trans fatty acids and distinction of cis-fatty acids of trans-fatty acids. Use of the substances according to 3 and 4 as pigments for glue colors and related colors such as watercolor paints and watercolors and colors for inkjet printer paper colors, Printing inks, inks and inks and other colors for painting and writing purposes and in paints. Use of the substances according to 3 and 4 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 3 and 4 in data memories, preferably in optical memories. Examples are systems like the CD or DVD discs. Use of the substances according to 3 and 4 as fluorescent dyes. Use of the substances according to 3 and 4 in OLEDS (organic light-emitting diodes). Use of the substances according to 3 and 4 in photovoltaic Attachments. Application of the dyes of 3 and 4 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 3 and 4 for staining of natural substances. Examples are paper, wood, straw, or natural Fiber materials such as cotton, jute, sisal, hemp, flax, hair and animal hair, wool or their transformation products such. B. the Viscose fiber, nitrate silk or copper rayon (rayon). Application of the dyes of 3 and 4 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 3 and 4 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 3 and 4 as pigments in electrophotography: z. B. for Trockenkopiersysteme (Xerox process) and laser printers (non-impact printing). Application of the dyes of 3 and 4 for Security marking purposes, the big chemical and photochemical stability and possibly also the fluorescence the substances of importance. This is preferred for Checks, check cards, banknotes coupons, documents, identification documents and the like, in which a special, unmistakable color impression should be achieved. Use of the dyes of 3 and 4 as an additive to other colors where a certain shade of color is achieved should, are particularly bright shades. Application of Dyes of 3 and 4 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 3 and 4 as fluorescent dyes for machine-readable markers, alphanumeric are preferred Imprints or barcodes. Application of the dyes of 3 and 4 for frequency conversion from light, z. B. from short-wave light of longer wavelength, to make visible light. Application of the dyes of 3 and 4 in display elements for many display, reference and marking purposes, z. B. passive display elements, information and traffic signs, such as Lights. Application of the dyes of 3 and 4 in inkjet printers in homogeneous solution as a fluorescent ink. Application of the dyes of 3 and 4 as starting material for superconducting organic materials. Application of the dyes of 3 and 4 for Solid fluorescent labels. Application of the dyes of 3 and 4 for decorative purposes. Application of the dyes of 3 and 4 for artistic purposes. Application of the dyes of 3 and 4 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). Use of Dyes of 3 and 4 as Fluorescent Dyes in Highly Sensitive Detection Ver drive. Application of the dyes of 3 and 4 as fluorescent dyes in scintillators. Application of the dyes of 3 and 4 as dyes or fluorescent dyes in optical light harvesting systems. Application of the dyes of 3 and 4 as dyes or fluorescent dyes in fluorescence solar collectors. Application of the dyes of 1 in liquid crystals for redirecting light. Application of the dyes of 3 and 4 as dyes or fluorescent dyes in fluorescence-activated displays. Application of the dyes of 3 and 4 as dyes or fluorescent dyes in cold light sources for light-induced Polymerization for the representation of plastics. Application of the dyes of 3 and 4 as dyes or fluorescent dyes for material testing, eg. B. at the production of semiconductor circuits. Application of the dyes of 3 and 4 as dyes or fluorescent dyes for the study of microstructures of integrated semiconductor devices. Application of the dyes of 3 and 4 as dyes or fluorescent dyes in photoconductors. Application of the dyes of 3 and 4 as dyes or fluorescent dyes in photographic processes. Application of the dyes of 3 and 4 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 3 and 4 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 3 and 4 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 3 and 4 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 3 and 4 as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams. Application of the dyes of 3 and 4 as dyes in dye lasers as a Q-switch switch. Application of the dyes of 3 and 4 as active Substances for nonlinear optics, e.g. For example the frequency doubling and frequency tripling of laser light. Application of the dyes of 3 and 4 as rheology improvers. Application of the dyes of 3 and 4 for leak testing closed systems.