DE102005034385A1 - Processes using exciton effect to reduce or increase fluorescence decay time, for frequency converters for fast optical communications systems, vary chromophore arrangement in multichromophore dyes to control electron transition moment - Google Patents

Abstract

Process (A) using exciton effect in multichromophore dyes for reducing fluorescence decay time comprises arranging chromophores so that electron transition moments enclose angle greater than 90[deg] and/or are shifted by more than half length of molecule or even also twisted with respect to one another. Examples are perylene and xanthene dyes, rhodamines, e.g. rhodamine B or 6G, fluorescein, eosin, porphyrins, coumarins, diaminostilbenes, aminonaphthalimides and terrylene- and quaterrylene-bisimides as higher homologues of perylene dyes. Independent claims are included for the following: (1) process (B) using exciton effect of multichromophore dyes for increasing fluorescence decay time; (2) use of process (B) for delaying and forming optical impulses; (3) processes (C-H, J, K) using specified mono-, bi-, tri- or tetra-chromophore perylene dyes, terrylene dyes or quaterrylene dyes for converting short-wavelength light, e.g. blue light, to fluorescent light of longer wavelength, e.g. yellow light; (4) use of all these processes in optical communication systems; (5) use in optical communication systems with optical fibers; (6) use in digital data transfer.

Description

introduction

The modern communication technologies require ever higher operating frequencies, so that future Systems will penetrate into the terahertz range.

As a result, the visible spectral range is becoming increasingly important: 500 nm of visible light corresponds to 600 terahertz (6 · 10 ¹⁴ Hz). For such a high frequency range special, new components are needed because it is difficult to access with the current electronic switching elements. Fluorescent dyes are particularly suitable for the frequency range, since they can pick up, buffer, process and re-radiate light of this high frequency; one can assume that such structures will replace the current electronic components in the future [1].

While the Processing of the recorded light basically with very high frequencies can be done, is the radiation process of fluorescent Structures relatively slow; so is the fluorescence decay time (fluorescence lifetime τ) of the strong color Fluorescent dye 1 already 4.95 ns (in chloroform) [2]. 1 presents a prototype [3,4] for highly stable, strong and strongly fluorescent dyes (Φ ≈ 100%) [5], but is required in terms of fluorescence decay time of modern communication technologies. A solution of the speed problem a significant step forward.

description

Basically you could to shortening the fluorescence decay time partially quench the fluorescence of 1 (Clear), but it loses a correspondingly high proportion of fluorescent light, so this is hardly a viable option. On the other hand the fluorescence decay time according to Förster [6] with the fluorescence quantum yield and linked to the molar absorption coefficient. Especially with fluorescence quantum yields near 100%, e.g. at 1, the fluorescence decay time is through limited the absorption coefficient. But since the latter at 1 with just under 90 000 is already very high, the prospects are one substantial further shortening the fluorescence decay time is small, so the impression of not being a first releasable Problem arises.

you However, it can be formally higher Achieve molar absorption coefficients when two or more Chromophores to a molecule connected. If one arranges these so that the electronic transition moments, at 1 the Connecting line of the nitrogen atoms, linearly behind one another, thus one achieves not only an addition of the transition moments, but beyond even a reinforcement by exciton interactions [7]. Comply with this condition Structures 2 and 3 and it is to ask to what extent this is affects the fluorescence decay time; the long dovetail leftovers in 2 or in 3 hinder an aggregation [8], so that the Fluorescence quantum yields remain high despite the large aromatic systems stay at almost 100%. The absorption coefficient of 3 is by the sum of the mentioned effects at nearly 420 000 [7].

The Measurement of the fluorescence decay time of 2 gave the surprising small value of 2.5 ns and that of 3 even only 2.0 ns; these are by far the smallest values for highly fluorescent perylene dyes have been found.

>>> 1 <<< The surprising measurement results of 2 and 3 show that it is possible to control the fluorescence decay time with unchanged high fluorescence quantum yield by exciton interactions. This is basically possible in two directions. As demonstrated in ref. [3], the type of exciton interaction in bi- and multichromophoric perylene dyes depends on the included angle Θ between the electronic transition moments; please refer 1 (at 2 and 3 is Θ 180 °). If Θ is less than 90 °, the exciton interaction is destructive and leads to a decrease in the absorption coefficient of the individual chromophores. At 90 °, both chromophores remain isolated from each other, so that the properties of the bichromophore are additively composed of the properties of the individual chromophores. If the angle is greater than 90 °, then there is a constructive exciton interaction with an increase in the absorption coefficient. Alternatively, the chromophores may be shifted from each other; d in 1 , If they are coplanar, the excitonic effect is destructive, they are sufficiently far apart from each other, then constructive, and finally one can also imagine mixed cases in which, for example, the chromophores are shifted from one another and include an angle of 0 ° to 180 ° or even beyond are twisted against each other.

If a destructive exciton interaction occurs at high fluorescence quantum yields, so be this is an extension of the fluorescence decay time. This situation finds its analogy in electronics as a monostable multivibrator (English "monoflop"), which is used in signal delay and signal shaping.Thus, this function can be achieved in the optical components by the destructive exciton interaction, so that a new building block of molecular signal processing technology is present.

A On the other hand, constructive exciton interaction leads to a reduction the fluorescence decay time and is for fast data transmission paths of special interest. This will be demonstrated here using the example of data transmission via optical fibers be demonstrated.

>>> 2 , <<< The blue-emitting GaN LEDs are currently available as fast optoelectronic components, but their spectral range is unfavorable for optical fibers made of PMMA. In the latter case, the attenuation in the yellow spectral range is the most favorable, so that longer communication paths are then possible in this spectral range. One could now use the dye 1 as a frequency converter for this purpose, since it absorbs light in the blue spectral range and converts it into the yellow spectral range; see the spectra of 2 , However, this is limited in the rate of data transfer by the fluorescence decay time of 1, which is 3.95 ns. On the other hand, using 2 as the frequency converter, the fluorescence decay time is shortened to 2.5 ns, and 3 even to 2.0 ns. This leads to a doubling of the transmission rate. If the chromophores were arranged even further, the absorption coefficient could in principle be increased even further, so that even the limit of 1 ns should be undershot.

The reduction of the fluorescence decay time by an increase in the absorption coefficient with the aid of exciton effects is not limited to a linear arrangement of the chromophores, but any orientation in space which leads to a constructive exciton interaction is fundamentally suitable for this purpose. Examples of these are the three following arrangements in which R ^{1 stands} for solubility-increasing radicals: B. long-chain sec-alkyl radicals [9,10] ("dovetail radicals") such as the 1-hexylheptyl radical or the 1-Heptyoctyl radical or for tert-butyl-bearing aromatics [11,12] as the 2,5-di tert-butylphenyl:

1st V-arrangement

The Chromophores in multichromophore arrangements do not necessarily need to be arranged linearly as in 2 or 3, when forming a V. as amplified in 4 the excitonic effect the absorption when the included angle between the transitional moments greater than 90 ° is. In connection 4 leads the interaction of the chromophores shifted to an additional long-wavelength Excitonenbande. Such arrangements are therefore also in principle for the Control of fluorescence decay time of interest.

2. Ring arrangements

A annular Arrangement of chromophores as in Figure 5 is another important way to control the fluorescence decay time. In 5, the angle is between the transitional moments 120 °, so that a constructive exciton effect occurs; you would in the same way six chromophores on the central phenyl radical bind, then it would be However, the included angle 60 °, and you would have a destructive Excitoneneffekt obtained by lowering the absorption coefficient. - This is to be considered in the design of suitable multichromophoric systems.

3. Tetrahedron

A interesting variant for the excitonic effect is the tetrahedral arrangement of chromophores such as in 6. Resulted by an included angle of transient moments of 109 ° a constructive Excitoneneffekt, so that the absorption coefficient reinforced becomes.

in the Contrary to 5, however, the structure 6 can light from all spatial directions and is therefore in the presence of multiple light sources or in diffuse light radiation of particular interest.

The here presented combinations can themselves among themselves combined into even larger units be so that there is a wide range of variations for all the requirements of communication technology.

The concept of control of the fluorescence decay time by excitonic interaction is not limited to the exemplified perylene dyes, although these are thus very clear spectra provide that they have only one electron transition in the visible spectral range. The concept can be applied to any fluorescent dyes; planning of these effects is often hampered by the fact that the position of the transition moments in relation to the molecular geometry is not known or that there are even several transitions with different orientations of the transition moments in the visible spectral range. Examples of further, strongly fluorescent chromophores are the xanthene dyes such as the rhodamines, in particular rhodamine B and rodamine 6G, fluorescein or eosin or else the porphyrins, coumarins, diaminostilbenes or aminonaphthalimides. The perylene dyes, perylene-3,4: 9,10-tetracarboxylic bisimides, may in particular be substituted in the positions 1, 6, 7 and 12 (so-called "bay positions") with optionally one to four donor groups such as amino groups, alkoxy or aryloxy groups Similarly, the higher analogues of the perylene dyes, the terrrylene bisimides (7) or the quaterrylene bisimides (8), in which the radicals R ^{1 have} the same meaning as in 4 to 6, can also be used and 8 at the so-called bay positions corresponding to the perylenebisimides may be substituted with donor groups, but for 7 but 1 to 8 and for 8 1 to 12.

you can remember the already very short fluorescence cooldown from 3 even further to shorten the speed of optical communication systems even further to increase. If this is done, as already mentioned, by a quenching process wants to reach, then bothers the loss of fluorescent light in such a procedure sets narrow limits. In particular, it is very disturbing that the loss of light according to the quench effect from the beginning begins, because the Decay characteristic remains more or less an e-function. Would be more interesting it, if at first the full fluorescence intensity would be available and then the fluorescence would decrease rapidly. This can be achieved by using a second light pulse. With the first light pulse, the dye is excited to fluoresce and it can follow a second light pulse after a short time, the causes a stimulated emission of the dye, as can be seen from the dye laser knows. This second light pulse then consumes the excited states, so that the fluorescence abruptly abates. Around To reach the stimulated emission one has to be in the range of the fluorescence spectrum radiate. Since this extends into the red spectral range, can do this e.g. a fast, red LED can be used. The corresponding delay between the two light pulses, e.g. with an electric Reach detour line for that ensures that the electrical signal e.g. 1 ns later on the red than on the blue LED hits; To convey an idea of the physical dimensions of such a delay line is recalled that the electric field travels in vacuo in 1 ns 30 cm. Is used as a dielectric material polytetrafluoroethylene (PTFE), which specializes in high frequencies due to its strong hydrophobicity is suitable, as a dielectric with a DK of about 2, so shortens the arrangement on 15 cm. It is interesting to use materials with one use very high DK, which then allow an even higher integration density. Therefor Dyes are also suitable for those with a DK up to more than 100 has been described [13].

The arrangement described last requires two different light-emitting diodes, thereby complicating the electrical part of such an arrangement. Using only one type of light emitting diode would bring further simplification. This can be done so that with the first light emitting diode a Functional unit containing a fluorescent dye, such as the dye 3, optically excited. With a delay of, for example, 1 ns, a second functional unit is optically excited, which likewise contains the dye or a similarly emitting dye. Its fluorescent light strikes the first unit but not the coupled optical system. The fluorescence light of the second unit is identical in its spectral distribution to that of the first unit and thus optimally suited to trigger a stimulated emission in the first unit. This effectively turns off the fluorescence of the first unit; the slower decay of the fluorescence of the second unit does not matter, since this light is not coupled out with; only the rapid increase in fluorescence in the second unit is decisive. The two units can be close together in one and the same material, if only it is ensured that the fluorescent light of the second unit does not hit the decoupling optics.

Here are the most accessible Light-emitting diodes for the optical stimuli first been specified. The same effects with the light stimulation below Use of lasers to achieve. The systems become more expensive, so this only for special applications should be used. Finally, can the optical excitation also be done using flash lamps.

• [1] H. Langhals, S. Saulich, Z. Naturforsch. 2003, 58b, 695–697.
• [2] L. B.-Å. Johansson, H. Langhals, 'Spectroscopic Studies of Perylene Fluorescent Dyes', Spectrochim. Acta 1991, 47A, 857–861.
• [3] H. Langhals, Helv. Chim. Acta. 2005, 88, 1309–1343.
• [4] H. Langhals, Heterocycles 1995, 40, 477–500.
• [5] H. Langhals, J. Karolin, L. B.-Å. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919–2922.
• [6] T. Förster, Fluoreszenz Organischer Verbindungen, 1. Aufl., Vandenhoeck & Ruprecht, Göttingen, 1951.
• [7] H. Langhals, W. Jona, Angew. Chem. 1998, 110, 998–1001; Angew. Chem. Int. Ed. Engl. 1998, 37, 952–955.
• [8] H. Langhals, R. Ismael, O. Yürük, Tetrahedron 2000, 56, 5435–5441.
• [9] H. Langhals, Ger. Patent DE 3703495 (February 5, 1987); Chem. Abstr. 1989, 110, P59524s.
• [10] H. Langhals, S. Demmig, T. Potrawa, J. Prakt. Chem. 1991, 333, 733–748.
• [11] H. Langhals, Ger. Patent 3016764 (April 30, 1980); Chem. Abstr. 1982, 96, P70417x.
• [12] H. Langhals, Nachr. Chem. Tech. Lab. 1980, 28, 716–718, Chem. Abstr. 1981, 95, R9816q.
• [13] H. Langhals, Chem. Phys. Lett. 1988, 150, 321–324.

The dyes mentioned can be used in homogeneous solution, such as in chloroform or ethyl acetate. However, this makes appropriate facilities more expensive because the dye solutions must be encapsulated. On the other hand, the dyes, such as 1 to 3 in macromolecular matrix, such as PMMA or polycarbonate, fluoresce equally strong as in homogeneous solution. It is therefore equally possible to use the dyes in a solid matrix, which considerably simplifies the handling and production of components. Because the dyes are thermally very stable, they can for example even be used in low-melting inorganic glasses, here are in particular phosphate glasses and borate glasses mentioned. Finally, it is possible to use the dyes even in high-melting silicate glasses, if these are prepared, for example, at low temperatures by the hydrolysis of the silicic acid orthomethyl or ethyl ester; The high chemical stability of the perylene dyes opposes this approach. In this case, however, the toxicity of methyl orthosilicate should be considered in particular.

• [1] H. Langhals, S. Saulich, Z. Naturforsch. 2003, 58b, 695-697.
• [2] LB-Å. Johansson, H. Langhals, Spectroscopic Studies of Perylene Fluorescent Dyes, Spectrochim. Acta 1991, 47A, 857-861.
• [3] H. Langhals, Helv. Chim. Acta. 2005, 88, 1309-1343.
• [4] H. Langhals, Heterocycles 1995, 40, 477-500.
• [5] H. Langhals, J. Karolin, LB-Å. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919-2922.
• [6] T. Förster, Fluorescence of Organic Compounds, 1st ed., Vandenhoeck & Ruprecht, Göttingen, 1951.
• [7] H. Langhals, W. Jonah, Angew. Chem. 1998, 110, 998-1001; Angew. Chem. Int. Ed. Engl. 1998, 37, 952-955.
• [8] H. Langhals, R. Ismael, O. Yürük, Tetrahedron 2000, 56, 5435-5441.
• [9] H. Langhals, Ger. Patent DE 3703495 (February 5, 1987); Chem. Abstr. 1989, 110, P59524s.
• [10] H. Langhals, S. Demmig, T. Potrawa, J. Prakt. Chem. 1991, 333, 733-748.
• [11] H. Langhals, Ger. Pat. No. 3,016,764 (April 30, 1980); Chem. Abstr. 1982, 96, P70417x.
• [12] H. Langhals, Nachr. Chem. Tech. Lab. 1980, 28, 716-718, Chem. Abstr. 1981, 95, R9816q.
• [13] H. Langhals, Chem. Phys. Lett. 1988, 150, 321-324.

Subject of the invention

• 1. A method characterized in that the Exciton effect on multichromophoric dyes for reduction The fluorescence cooldown is used by the chromophores be arranged so that the electronic transition moments an angle from bigger than Include 90 ° or by more than half the length of the molecule against each other are shifted or both fulfilled is or even twisted against each other. Examples for such Dyes are the perylene dyes, the xanthene dyes and especially Rhodamine such as Rhodamine B or Rhodamine 6G, Fluorescein or eosin or even the porphyrins, the coumarins, Diamino stilbene or the aminonaphthalimides; finally are here as higher Homologues of perylene dyes, terylenebisimides and quaterrylenebisimides to call.
• 2. A method characterized in that the exciton effect is used in multichromophoric dyes to increase the fluorescence decay time by arranging the chromophores so that the electronic transition moments include an angle of less than 90 ° or shifted by less than half the molecule length, or both is fulfilled or even twisted against each other. Examples of such dyes are the perylene dyes, the xanthene dyes and especially the rhodamines such as rhodamine B or rhodamine 6G, fluorescein or eosin or the porphyrins, coumarins, diaminostilbene or aminonaphthalimides; finally are Here, as higher homologues of perylene dyes, mention the terrylenbisimides and the quaterrylenebisimides.
• 3. Process characterized in that perylene dyes of the general formula 9 for the conversion of kurzwelligem, eg blue light, in longer-wave fluorescent light, in particular yellow light, are used.
  
  in which the radicals R ¹ to R ^{6 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 carbonyl groups , Oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡C groups 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2 , 5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3- , 2,6- or 2,7-disubstituted naphthalene radicals in which one or two CH groups may be replaced by nitrogen atoms, 1,2-, 1,3-, 1,4-, 1,5-, 1,6 -, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10 disubstituted anthracene residues in which one or two CH groups can be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group or a linear alkyl chain with up to 18 C atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9, 2, 10 or 9,10-disub substituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which one to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CH = CH groups in which a CH unit can also be replaced by a nitrogen atom, acetylenic C ≡C groups 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9, 2, 10-od he 9,10-disubstituted Anthracenreste in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or of the quaternary C atoms can be linked in pairs to form rings, such as cyclohexane rings.
• 4. Process characterized in that bichromophoric perylene dyes of the general formula 10 for the conversion of short-wave, eg blue light, in longer-wave fluorescent light, in particular yellow light, are used.
  
  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 i CH groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group or a linear alkyl chain with up to 18 C atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9, 2, 10 or 9,10-disub substituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which one to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit can also be replaced by a nitrogen atom, acetylenic C ≡C groups 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9, 2, 10-od he 9,10-disubstituted Anthracenreste in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or of the quaternary C atoms can be linked in pairs to form rings, such as cyclohexane rings.
• 5. A method characterized in that trichromophoric perylene of the general formula 11 for the conversion of kurzwelligem, eg blue light, in longer wavelength fluorescent light, in particular yellow light, are used.
  
  in which the radicals R ¹ to R ^{14 may be the} same or different and may independently of one another have hydrogen or the meaning given under 4.
• 6. A method characterized in that trichromophoric perylene of the general formula 4 for the conversion of kurzwelligem, eg blue light, in longer wavelength fluorescent light, in particular yellow light, are used.
  
  in which the radicals R ^{1 may be the} same or different and may independently of one another have hydrogen or the meaning given under 4.
• 7. A method characterized in that trichromophoric perylene dyes of the general formula 5 for the conversion of kurzwelligem, eg blue light, in longer wavelength fluorescent light, in particular yellow light, are used.
  
  in which the radicals R ^{1 may be the} same or different and may independently of one another have hydrogen or the meaning given under 4.
• 8. A process characterized in that trichromophoric perylene dyes of the general formula 6 for the conversion of kurzwelligem, eg blue light, in longer wavelength fluorescent light, in particular yellow light, are used.
  
  in which the radicals R ^{1 may be the} same or different and may independently of one another have hydrogen or the meaning given under 4.
• 9. A method characterized in that terrylene dyes of the general formula 12 for the conversion of short-wave, eg blue light, are used in longer wavelength fluorescent light.
  
  in which the radicals R ¹ to R ^{10 may be the} same or different and may independently of one another have hydrogen or the meaning given under 4.
• 10. A method, characterized in that Quaterrylenfarbstoffe the general formula 13 for the conversion of short-wave light, are used in longer wavelength fluorescent light.
  
  in which the radicals R ¹ to R ^{14 may be the} same or different and may independently of one another have hydrogen or the meaning given under 4.
• 11. Method characterized in that light from light-emitting diodes, preferably of blue gallium nitride light-emitting diodes for optical excitation the dyes according to 1 to 10 is used.
• 12. A method characterized in that light from laser light sources for the optical excitation of the dyes is used after 1 to 10.
• 13. Method characterized in that light from flash lamps for the optical excitation of the dyes is used after 1 to 10.
• 14. A method characterized in that the fluorescence decay time by a second light pulse in the wavelength range of the fluorescence spectrum shortened by stimulated emission becomes. Light sources can e.g. For 1 to 6 be red LEDs.
• 15. Method characterized in that as the light source for the stimulated Emission of the same dye after 1 to 10 is used as to generate the light pulse, but this is delayed delayed, with time delays in the nanosecond range.
• 16. A method characterized in that the dyes after 1 to 10 homogeneous in solvents be used. Suitable solvents are chloroform, ethyl acetate or ethanol.
• 17. A method characterized in that the dyes after 1 to 10 in macromolecular. Organic matrix are used. Suitable materials are e.g. Polymethyl methacrylate (PMMA), polycarbonate, but also materials like polypropylene, polystyrene, polyester or Polyamide or silicone are conceivable.
• 18. Process characterized in that the dyes after 1 to 10 in inorganic glasses are used, preferably low-melting glasses such as phosphate glasses or borate glasses, but also high-melting silicate glasses, if these at low Temperatures are produced by the hydrolysis of silicic acid esters.
• 19. Application of the methods according to 1 to 18 in optical communication systems.
• 20. Application of the methods according to 1 to 18 in optical communication systems using optical fibers. Preferred materials for optical fibers are polymethymmethacrylate (PMMA), polycarbonate and inorganic glasses like silicate glasses, phosphate glasses and borate glasses.
• 21. Application of the methods according to FIGS. 1 to 18 for digital information transmission.
• 22. Application of the method according to FIG. 2 for optical pulse delay and Pulse shaping.

LIST OF REFERENCE NUMBERS

• 1 , Typical arrangements of transition moments in bichromophores. Θ: included angle, d: lateral displacement.
• 2 , UV / Vis absorption (left) and fluorescence spectrum (right) of 1.

Claims (22)

A method characterized in that the exciton effect is used in multichromophoric dyes to reduce the fluorescence decay time by arranging the chromophores such that the electronic transient moments are at an angle greater than 90 ° or offset from each other by more than half the molecule length or both are met or even twisted against each other. Examples of such dyes are the perylene dyes, the xanthene dyes and especially the rhodamines such as rhodamine B or rhodamine 6G, fluorescein or eosin or the porphyrins, coumarins, diaminostilbene or aminonaphthalimides; after all, here are higher than Ho Mologens of the perylene dyes to call the Terylenbisimide and Quaterrylenbisimide. Process characterized in that the exciton effect for multichromophoric dyes to increase the fluorescence decay time is used by arranging the chromophores so that the electronic transitional moments include an angle of less than 90 ° or less than half the molecule length against each other are shifted or both fulfilled is or even twisted against each other. Examples for such Dyes are the perylene dyes, the xanthene dyes and especially Rhodamine such as Rhodamine B or Rhodamine 6G, Fluorescein or eosin or even the porphyrins, the coumarins, Diamino stilbene or the aminonaphthalimides; finally are here as higher Homologs of perylene dyes are terrylenebisimides and quaterrylenebisimides to call. Process characterized gekennzeichnet that perylene dyes of the general formula 9 for the conversion of short-wave, eg blue light, in longer wavelength fluorescent light, in particular yellow light used.

in which the radicals R ¹ to R ^{6 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 carbonyl groups , Oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡C groups 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2 , 5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3- , 2,6- or 2,7-disubstituted naphthalene radicals in which one or two CH groups may be replaced by nitrogen atoms, 1,2-, 1,3-, 1,4-, 1,5-, 1,6 -, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10 disubstituted anthracene residues in which one or two CH groups can be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group or a linear alkyl chain with up to 18 C atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9, 2, 10 or 9,10-disub substituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which one to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit can also be replaced by a nitrogen atom, acetylenic C ≡C groups 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9, 2, 10-od he 9,10-disubstituted Anthracenreste in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or of the quaternary C atoms can be linked in pairs to form rings, such as cyclohexane rings. A process characterized in that bichromophoric perylene dyes of the general formula 10 for the conversion of short-wave, eg blue light, in longer-wave fluorescent light, in particular yellow light, are used.

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 i CH groups may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups can each independently be replaced on the same C atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano group or a linear alkyl chain with up to 18 C atoms, in which a to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9, 2, 10 or 9,10-disub substituted anthracene residues in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl radicals can each be replaced independently of the same C atoms by the halogens fluorine, chlorine, bromine or iodine or or cyano groups or linear alkyl chains having up to 18 carbon atoms, in which one to 6 CH ₂ units can be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit can also be replaced by a nitrogen atom, acetylenic C ≡C groups 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5- disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1 , 4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2 , 9, 2, 10-od he 9,10-disubstituted Anthracenreste in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents, the free valencies of the methine groups or of the quaternary C atoms can be linked in pairs to form rings, such as cyclohexane rings. A process characterized in that trichromophoric perylene dyes of the general formula 11 for the conversion of short-wave, eg blue light, in longer-wave fluorescent light, in particular yellow light, are used.

in which the radicals R ¹ to R ^{14 may be the} same or different and may independently of one another have hydrogen or the meaning given under 4. A process characterized in that trichromophoric perylene dyes of the general formula 4 for the conversion of short-wave, eg blue light, in longer-wave fluorescent light, in particular yellow light, are used.

in which the radicals R ^{1 may be the} same or different and may independently of one another have hydrogen or the meaning given under 4. A process characterized in that trichromophoric perylene dyes of the general formula 5 for the conversion of short-wave, eg blue light, in longer-wave fluorescent light, in particular yellow light, are used.

in which the radicals R ^{1 may be the} same or different and may independently of one another have hydrogen or the meaning given under 4. A process characterized in that trichromophoric perylene dyes of the general formula 6 for the conversion of short-wave, eg blue light, in longer-wave fluorescent light, in particular yellow light, are used.

in which the radicals R ^{1 may be the} same or different and may independently of one another have hydrogen or the meaning given under 4. A process characterized in that terrylene dyes of the general formula 12 for the conversion of short-wave, for example, blue light, are used in longer wavelength fluorescent light.

in which the radicals R ¹ to R ^{10 may be the} same or different and may independently of one another have hydrogen or the meaning given under 4. A method characterized in that Quaterrylenfarbstoffe the general formula 13 for the conversion of short-wave light, are used in longer wavelength fluorescent light.

in which the radicals R ¹ to R ^{14 may be the} same or different and may independently of one another have hydrogen or the meaning given under 4. Method characterized in that light from Light-emitting diodes, preferably of blue gallium nitride LEDs for optical excitation of the dyes is used after 1 to 10. Method characterized in that light from Laser light sources for the optical excitation of the dyes according to 1 to 10 is used. Method characterized in that light from Flash lamps for the optical excitation of the dyes according to 1 to 10 is used. Method characterized in that the fluorescence decay time by a second light pulse in the wavelength range of the fluorescence spectrum shortened by stimulated emission becomes. Light sources can e.g. For 1 to 6 be red LEDs. Method characterized in that as the light source for the stimulated emission of the same dye used after 1 to 10 is like the generation of the light pulse, this stimulated but with a time delay will, with time delays in the nanosecond range. Process characterized in that the dyes after 1 to 10 homogeneous in solvents be used. Suitable solvents are chloroform, ethyl acetate or ethanol. Process characterized in that the dyes after 1 to 10 in macromolecular. Used organic matrix become. Suitable materials are e.g. Polymethyl methacrylate (PMMA), Polycarbonate, but also materials such as polypropylene, polystyrene, Polyester or polyamide or silicone are conceivable. Process characterized in that the dyes are used after 1 to 10 in inorganic glasses, preferably low melting glasses like phosphate glasses or borate glasses, but also high-melting silicate glasses, if these at low Temperatures are produced by the hydrolysis of silicic acid esters. Application of the method according to 1 to 18 in optical Communications systems. Application of the method according to 1 to 18 in optical Communication systems using optical fibers. preferred Materials for Optical fibers are polymethymmethacrylate (PMMA), polycarbonate and inorganic glasses like silicate glasses, phosphate glasses and borate glasses. Application of the methods according to FIGS. 1 to 18 to the digital Information transfer. Application of the method according to FIG. 2 for optical pulse delay and Pulse shaping.