DE102015000815A1 - Alkylketo-oligothiophenes and their use in high speed optical signal transmission - Google Patents

Abstract

Alkylketo-terminated oligothiophenes are prepared from the oligothiophenes and carboxylic acid chlorides in Friedel-Crafts reactions and are characterized by significant fluorescence quantum yields as well as short fluorescence decay times and are therefore useful as light transducers in optical signal transmission systems, such as. As optical slip rings, particularly suitable.

Description

State of the art

High-speed digital information transmission is becoming increasingly important. Optical transmission paths are of particular interest because they have many advantages. Frequency and directional converters and optical slip rings [1] are required for non-contact transmission of freely rotatable elements. Fluorescent dyes are attractive for such functional entities. However, their working frequency is limited by the fluorescence decay time, which is about 5 ns in the vast majority of strongly fluorescent substances [2]. However, this is a hurdle for the gigabit gap and it would be of interest to use highly fluorescent dyes whose fluorescence decay time is well below this value.

task

The object of the present invention was to develop strongly fluorescent dyes with short fluorescence decay times, large Stokes shifts and high lightfastness.

description

According to a theory by Förster [3, 4], fluorescence quantum yields, molar extinction coefficients, and fluorescence decay times are related by the fluorescence decay time of strongly fluorescent substances given by the natural transition probability of the respective electron transition, which is reflected by the extinction coefficient. For strongly fluorescent substances, such. As the perylene dyes, with high molar extinction coefficients of 100000 L · mol ^-1 · cm ^-1 , the mentioned about 5 ns fluorescence decay time from the natural probability for electron transfer. Although a reduction in the fluorescence quantum yield can in principle be achieved by reducing the fluorescence decay time, the luminous efficacy also decreases. Since a significant increase in the extinction coefficient is difficult to achieve, it seems hopeless to develop useful fluorescent dyes with much shorter cooldowns.

Remarkably, in previous work [5, 6] it was found that 2,5-oligothiophenes [7, 8] with adamantyl end groups fluoresce with very short decay times; In the case of unsubstituted 3- and 4-positions, the Stokes shift of the dyes is also increased by a dynamic process. These connections are therefore fundamentally interesting for optical information transmission systems. The UV / Vis spectra of such a series of compounds change with the number of thiophene units in relatively large increments; In contrast, a fine optical adjustment in various applications would be desirable. Since the 3 and 4 positions of the thiophene units must remain unsubstituted to achieve a large Stokes shift, there are no further variations.

We have studied the extension of the chromophore of oligothiophenes with terminal carbonyl groups, of which little is known [9, 10]; Although one should expect an influence on the UV / Vis spectra, but also a significant deterioration in the properties of an optical data transmission, because the incorporation of carbonyl groups in chromophores often leads to a significant reduction in fluorescence quantum yields by promoting the inter-system Crossing Process (ISC) [11]. In addition, the chromophore of the oligothiophenes is disturbed by carbonyl groups, and this could negatively affect the short fluorescence lifetimes. In fact, in a one-sided substitution with a methyl ketone group, an increase in fluorescence lifetime was found to be 1.6 ns (in methanol at 49% fluorescence quantum yield) [12].

We have synthesized diketo-oligothiophene, of which only a few studies are available [13, 14], possibly even on the diacetyl derivatives (carboxylic acids and carboxylic acids are still known for carbonyl derivatives [15]). The unprecedented terthiophene 1, in which we expected the terminal tert-butyl groups to have an increased solubility [16], was obtained analytically pure by a Friedel-Crafts acylation of the unsubstituted terthiophene with pivaloyl chloride in a remarkably high yield of 79%, although a two-fold reaction takes place on terthiophene, from which one expects a reduction in yield. Low levels of byproducts that could interfere with precise optical applications could be removed by simple chromatography because of the high solubility of the material. In an analogous manner, propionyl chloride was converted to 2, which was obtained analytically pure in an even higher, astonishing yield of 93%. An extension of the terminal residues to Pentanonylderivat 3 was also smooth, but the purification proved to be considerably more difficult and eventually led to 17% reagent-free substance.

As an alternative, perfluoroalkyl-terminated keto-oligothiophenes were synthesized in an analogous manner, which were expected to have particular solvent effects and optical properties; Surprisingly, under the reaction conditions, only a simple acylation of dithiophene to 4 and of trithiophene to 5 occurred with perfluorobutyryl chloride. Obviously, the electron cycle through a perfluoroalkycarbonyl group is already so great that a second substitution is made considerably more difficult. Table 1. Optical properties of the oligothiophene ketones in chloroform. dye λ _Abs in nm λ _Flu. in nm ε ^a) Φ ^b) τ in ns ^c) Δλ in nm Stokes shift in eV 1 410.2 (413.1) ^d) 494.3 (484.3) ^e) 43800 12:54 0.40 (0.39) ^e) 82.8 (71.2) ^e) 0.50 (0.44) ^e) 2 406.2 (439.4) ^d) 490.4 (481.6) ^e) 45300 12:52 0.39 (0.39) ^e) 84.6 (42.2) ^e) 0.53 (0.25) ^e) 3 409.4 494.3 34700 0.71 12:40 85.7 12:53 4 384.0 447.7 23300 0.62 1:45 62.9 12:45 5 432.2 (465.5) 528.8 (520.4) ^e) 42200 12:47 2.50 (1.61) ^e) 80.5 (54.9) ^e) 0.42 (0.28) ^e) a) Molar extinction coefficient. b) fluorescence quantum yield. c) fluorescence decay time. d) fluorescence excitation spectrum in PMMA. e) In PMMA.

The optical properties of 1 are surprising in several respects; see Table 1. Thus, a remarkably high fluorescence quantum yield of 54% is found, which exceeds that of other oligothiophenes, and for the other carbonyl derivatives also consistently high fluorescence quantum isomers are observed; Thus, the carbonyl groups in 1 did not adversely affect but even promoted the intensity of fluorescence. Also surprising is the short fluorescent luminescent time of 1 of only 0.40 ns (Tab. 1 and 2 ), which corresponds to that of the alkyl oligothiophenes; extension of the chromophore by two carbonyl groups does not adversely affect the short fluorescence decay time. This is unexpected because a much longer fluorescence leaching time has been reported for simple carbonyl derivatives [12]. Even the high Stokes shift of the oligothiophenes unsubstituted in positions 3 and 4, which has been attributed to a dynamic process after optical excitation [5], remains at 1 (absorption maximum at 410.2 nm and maximum fluorescence at 494.3 nm), as shown 1 can be seen. Since the large Stokes shift also occurs almost unchanged in PMMA matrix as organic glass (absorption 413.1 and fluorescence 484.3 nm, see 3 ), one can assume that a dynamic after the optical excitation is possible to a similar extent also in solid organic glass matrix. The assumed lateral expansion and partial planarization of 1 as relaxation after its optical excitation is obviously small enough and the mobility of the matrix is large enough to allow such a process; the spherical cap tert-butyl end groups may be particularly favorable for this purpose (ball joint effect). Favorable for applications of Dye 1 is its easy solubility, which makes it particularly suitable for homogeneous media, and its unexpectedly high lightfastness, which is evidenced by the absence of photobleaching effects in direct sunlight over many months. Its chemical resistance is also very high, because it can, for. B. can be used without decomposition under the conditions of free-radical polymerization at just under 100 ° C. The lack of enolizable protons may also be responsible for the substance's long-term stability. The UV / Vis absorption spectrum (see 1 ) is shifted bathochromium over the absorption of alkylterthiophene, [5] complementing the dialkyl-oligothiophenes. Likewise, the fluorescence spectrum is bathochromically shifted. The latter achieves an optimum range for a PMMA light guide at 1.

The ethyl derivative 2 is also useful for the applications mentioned, although its solubility and durability are slightly less than that of FIG. In contrast, it can be prepared in a much higher yield of analyte. However, its Stokes shift in solid polymer glass matrix decreases considerably; see Tab. 1 and 5 and 7 , The fluorescence exposure time is identical to that of 1 ( 6 ) and also does not change in polymer matrix; 8th , Further extension of the terminal alkyl chains to Butyderivat 3 offers no further advantages for the applications, because the optical properties remain similar; 9 and 10 , However, the workup is considerably more complicated and resulted in only 17% of reagent-free substance. Perfluorination to the mono-ketosubstituted oligothiophenes results in a marked bathochromic shift in absorbance and fluorescence (384.0 and 447.7 nm at 4 and 432.2 and 528.8 nm at 5, see 11 and 13 ) and therefore complement the dyes 1 to 3. However, the fluorescence decay times are significantly longer than those of the diketoderivate; Tab. 1 and 12 and 14 , But they remain relatively short with 1.5 to 2.5 ns; the derivatives 4 and 5 thereby spectrally complement the dyes 1 to 3. The Stokes shift is significantly smaller in solid PMMA glass matrix and the fluorescence decay time of 5 is slightly shortened; see Tab. 1, 15 and 16 , The light fastnesses and solubilities of 4 and 5 are high, but the latter do not reach those of 1.

The diketone 1 and homologous compounds as well as monoketones are generally of interest as oligothiophenes in materials science [17, 18] [19]. 1 ideally meets all requirements for digital signal transmission in the gigabit range. In particular, its short fluorescence decay time, but also its strong fluorescence and its large Stokes shift are of great importance for applications in optical slip ring systems. Here, the ketooligothiophenes are expediently used less in homogeneous solution than in transparent polymer matrix [20, 21]; the high solubility and lipophilicity is of particular advantage. Examples of suitable polymer materials are PMMA, polycarbonate, polystyrene, transparent silicones and transparent polyfluoroalkanes and polyfluoroethers. PMMA (Plexiglas) is to be preferred because of its high transparency (minimum attenuation) in the relevant spectral range.

The dyes 1 to 5 can be introduced in various ways in the polymer materials, such as. B. by mixing with polymer materials, eg. B. as granules, and melting using extrusion or injection molding, and finally by the matrix with the common dissolution and evaporation of the solvent. The dyes can also be dissolved in the monomer, which is then polymerized, such as. As methyl methacrylate to polymethylmethacrylate. Surprisingly, the radical polymerization does not cause any problems, not even though the dye is sulfur-containing and has been used at temperatures up to 70 ° C. Finally, the dye may also be solvent in the polymeric materials be diffused. The choice of the doping method depends on the respective technological boundary conditions.

In the case of a fluorescence excitation, it can be assumed that fluorescence has decayed virtually completely after 10 half-lives, since then there is less than 1 percent residual fluorescence fluorescence. In the concrete case this would correspond to a repetition time constant of less than 3 ns. On the other hand one can accept a partial fluorescence saturation and adapt the detection system. You then get even shorter repeating times. The Stokes shifts of the dye is relatively large. This basically opens up the possibility of depopulating the optically excited state. One would proceed in such a way that it is optically excited in the absorption region of the dye by a light pulse and the fluorescence detected immediately thereafter. With a second light pulse at longer wavelengths in the range of fluorescence, one can generate stimulated fluorescence and thus depopulate the excited state (see How Dye Lasers Work). The sequence of the two pulses can be short, since substantial parts of the fluorescence are already obtained within the first half-life. In principle, it is possible to achieve a repeating constant of less than 0.4 ns in the concrete examples. The transmission of the information content can be increased by suitable modulation methods in a manner known per se.

The information transfer can be carried out according to the principle of the fluorescence solar collector [22], in which a highly refractive material such as Plexiglas is homogeneously colored with a fluorescent dye; This material can form a plane-parallel plate or a round light guide, which can also be arranged in the form of a round optical slip ring to ensure signal transmission from all directions. Light can penetrate from all spatial directions with refraction in the polymer material and is absorbed by the fluorescent dye dissolved there. The fluorescent light is radiated isotropically in all spatial directions, but in a small proportion it can only leave it when it hits the surface steeply (see critical angle of total reflection). The main part hits flat on the surface, is thrown back into the material by total reflection and guided there to the edge surface. In the case of optical slip rings, mechanical robustness can be radiated from all directions of rotation with respect to the light guide and detected at the end of the light guide.

conclusion

Oligothiophenes can be converted via a Friedel-Crafts acylation into the terminal diketo derivatives, which are characterized by high fluorescence quantum yields and short fluorescence decay times. They can advantageously be used in light-collecting systems based on the principle of the fluorescence solar collector, in particular for optical slip ring systems. Dye 1 ideally combines a short fluorescence decay time of 0.4 ns, which is also retained in polymer matrix, with a large Stokes shift and easy solubility in lipophilic media. The spectral data fits well with the technology of laser sources, light guides and detectors. The short fluorescence decay time is of particular interest for optical slip ring systems because of the extremely high data transmission rates in the gigabit range. The high chemical and photochemical stability of the substance allows long working times of such arrangements.

Experimental part

• General. IR Spectra: Perkin Elmer 1420 Ratio Recording Infrared Spectrometer, FT 1000; UV / Vis spectra: Varian Cary 5000; Fluorescence spectra: Varian Cary Eclispe; Fluorescence lifetimes: PicoHarp 300 from PicoQuant, λ _Anr. = 403 nm; NMR spectroscopy: Varian Vnmrs 600 (600 MHz); Mass spectrometry: Finnigan MAT 95. Fluorescence quantum yields were determined analogously to Ref. [23].
  

1,1 '- ([2,2': 5 ', 2''- terthiophene] -5,5''- diyl) bis (2,2-dimethylpropan-1-one) (1): In a dry glass apparatus 2.2 ': 5', 2 '' - terthiophene (62.3 mg, 0.250 mmol) was dissolved under argon in 1.0 mL carbon disulfide, cooled to 0 ° C. while stirring, with 2,2-dimethylpropanoyl chloride (0.30 mL, 302 mg, 2.50 mmol) and aluminum chloride (83.3 mg, 0.625 mmol) are added (immediately violet coloration), allowed to warm to room temperature, after 1 h and then after 2 h reaction time with (each 83.3 mg, 0.625 mmol), after 3 h in vacuo freed of the volatile compounds, admixed with 5 ml of saturated ammonium chloride solution, extracted with chloroform (2 × 10 mL), evaporated to dryness with the rotary evaporator and purified by column chromatography (silica gel, chloroform / iso-hexane 2: 1). Y. 82.0 mg (0.197 mmol, 79%) of yellow solid, mp 206 ° C. IR (ATR): ν ~ = 2968, 1633 (s), 1506, 1466, 1436 (s), 1363, 1327, 1278, 1196, 1175, 1065, 1024, 914, 854, 820, 792 (s), 748 cm ^-1 . ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 7.69 (d, ³ J = 4.1 Hz, 2H), 7.24 (s, 2H), 7.18 (d, ³ J = 4.0 Hz, 2H), 1.41 (s , 18H) ppm. ¹³ C-NMR (100 MHz, CDCl _3): δ = 199.0, 143.7, 141.7, 137.3, 133.3, 126.8, 124.7, 44.4, 28.69 ppm. UV / Vis (CHCl _3): λ _max (ε) = 410.2 nm (43800). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 465.6 (0.98), 494.3 (1.00) nm. Fluorescence quantum eff. (CHCl ₃ , λ _ex = 410.2 nm, E _{410.2 nm / 1 cm} = 0.246, standard: perylene-3,4: 9,10-tetracarboxylic acid tetramethyl ester with Φ = 1.00): 0.54. MS (70 eV, EI): m / z = 416.07 (M ⁺ ), 359.03 (M ⁺ - C ₄ H ₉ ), 331.05 (M ⁺ - C ₅ H ₉ O), 287.10, 246.03. HRMS (EI): C ₂₂ H ₂₄ O ₂ S ₃ m / z = Ber. 416.0933, Gef. 416.0930, Δ = -0.3 mmu. CHNS: Ber. C: 63.42, H: 5.81, S: 23.09, Gef C: 62.04, H: 5.91, S: 20.60.

1,1 '- ([2,2': 5 ', 2''- terthiophene] -5,5''- diyl) bis (ethyl ketone) (2). In a dry glass apparatus, 2,2 ': 5', 2 '' - terthiophene (62.1 mg, 0.250 mmol) was dissolved under argon in 1.0 mL carbon disulfide, cooled with stirring to 0 ° C, with propionic acid chloride (0.22 mL, 230 mg, 2.5 mmol) and aluminum chloride (83.3 mg, 0.625 mmol) (immediate red coloration), allowed to warm to room temperature, after 1 h and then after 2 h reaction time with additional aluminum chloride (83.3 mg each, 0.625 mmol), 3 hours, evaporated in vacuo (12 mbar), admixed with saturated ammonium chloride solution (5 ml), extracted with chloroform (2 × 10 ml), evaporated in vacuo with the rotary evaporator and purified by column chromatography (silica gel, chloroform / iso-hexane 2: 1). , Y. 84.0 mg (0.233 mmol, 93%) of yellow solid. Mp: 222 ° C, IR (ATR): ν ~ = 2977, 2938, 2877, 1655 (s), 1507, 1441, 1412, 1378, 1354, 1254, 1221, 1086, 1060, 912, 882, 854, 787 (vs), 744, 724, 666 cm ^-1 . ¹ H-NMR (400 MHz, CDCl _3): δ = 7.63 (d, ³ J = 4.0 Hz, 2H), 7.29 (s, 2H), 7.24 (d, ³ J = 4.0 Hz, 2H), 2.92 (q , ³ J = 7.3 Hz, 4H), 1.21 (t, ³ J = 7.3 Hz, 6H) ppm. ¹³ C-NMR (100 MHz, CDCl _3): δ = 133.0, 127.0, 125.2, 32.7, 8.8 ppm. UV / Vis (CHCl ₃ ): λ _max (ε) = 406.2 nm (68600). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 463.3 (0.91), 490.4 (1.00) nm. Fluorescence quantum eff. (CHCl ₃ , λ _ex = 406.2 nm, E _{406.2 nm / 1 cm} = 0.0248, reference: perylene-3,4: 9,10-tetracarboxylic acid tetramethyl ester with Φ = 1.00): 0.52. MS (70 eV, EI) m / z (%) = 360 (M ⁺ ), 331 (M - C ₂ H ₅ ), 303 (M - C ₃ H ₅ O), 259. HRMS (EI), C ₁₈ H ₁₆ O ₂ S ₃ m / z = Ber. 360.0312, Gef. 360.0314, Δ = +0.2 mmu. C ₁₈ H ₁₆ O ₂ S ₃ (360.5): Calcd. C: 59.97, H: 4.47, S: 26.68, Gef. C: 60.20, H: 4.53, S: 26.82.

1,1 '- ([2,2': 5 ', 2''- terthiophene] -5,5''- diyl) bis (pentan-1-one) (3): In a dry glass apparatus, 2.2 ': 5', 2 '' - Terthiophen (62.0 mg, 0.250 mmol) under argon dissolved in 1.0 mL carbon disulfide, cooled with stirring to 0 ° C, with pentanoyl chloride (0.30 mL, 301.5 mg, 2.50 mmol) and aluminum chloride (83.3 mg , 0.625 mmol) (immediately reddish color), warmed to room temperature, after 1 h and then after 2 h with additional aluminum chloride (83.3 mg, 0.625 mmol), after 3 h in vacuo of volatile compounds, with 5 mL saturated ammonium chloride solution, extracted with chloroform (2 × 10 mL), purified by rotary evaporation with a column chromatography (silica gel, chloroform / iso-hexane 1: 1 to remove by-products and chloroform for elution). Y. 18.0 mg (0.0433 mmol, 17%) of orange solid. Mp 208 ° C. IR (ATR): ν ~ = 2960, 2929, 2872, 1655, 1507, 1464, 1445, 1409, 1380, 1347, 1259, 1209, 1088, 1016 (s), 930, 858, 789 (s), 751, 735, 701, 673 cm ^-1 . ¹ H-NMR (400 MHz, CDCl ₃ ): δ = 7.62 (d, ³ J = 4.0 Hz, 2H), 7.29 (s, 2H), 7.24 (d, ³ J = 4.0 Hz, 2H), 2.88 (t , ³ J = 7.3 Hz, 4H), 1.75-167 (m, 4H), 1.52-1.37 (m, 4H), 0.96 (t, ³ J = 7.3 Hz, 6H) ppm. ¹³ C-NMR (100 MHz, CDCl _3): δ = 193.5, 144.5, 143.7, 137.5, 133.1, 127.0, 125.2, 39.2, 27.4, 23.0, 14.2, 1.3 ppm. UV / Vis (CHCl _3): λ _max (ε) = 409.4 nm (34700). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 464.2 (0.98), 491.2 (1.00) nm. Fluorescence quantum eff. (CHCl ₃ , λ _ex = 409.4 nm, E _{409.4 mm / 1 cm} = 0.421, standard: perylene-3,4: 9,10-tetracarboxylic acid tetramethyl ester with Φ = 1.00): 0.71. MS (70 eV, EI): m / z = 416.02 (M ⁺ ), 374.00 (M ⁺ - C ₃ H ₆ ), 331.98 (M ⁺ - C ₆ H ₁₂ ), 316.97 (M ⁺ - C ₇ H ₁₅ ) , HRMS (EI): C ₂₂ H ₂₄ O ₂ S ₃ m / z = 416.0933 about (M ^+), found.. 416.0934, Δ = +0.1 mmu.

1 - ([2,2'-Bithiophene] -5-yl) -2,2,3,3,4,4,4-heptafluorobutan-1-one (4): In a dry glass apparatus, 2,2'- Bithiophene (257 mg, 1.54 mmol) was dissolved under argon in 3.0 mL carbon disulfide, cooled to 0 ° C. with stirring, admixed with heptafluorobutyryl chloride (2.31 mL, 3.59 g, 15.5 mmol) and aluminum chloride (480 mg, 3.85 mmol) (immediate red coloration ), allowed to warm to room temperature, after 1 h and then after 2 h reaction time with additional aluminum chloride (480 mg, 3.85 mmol), after 3 h in vacuo of volatile compounds, with 5 mL of saturated ammonium chloride solution, extracted with chloroform (2 × 10 mL), evaporated with the rotary evaporator and purified by column chromatography (silica gel, 1st chloroform, 2nd chloroform / iso-hexane 1: 3, 3rd iso-hexane). Y. 156 mg (0.431 mmol, 30%) of yellow acicular crystals, mp 58 ° C. IR (ATR): ν ~ = 3118, 1663 (s), 1540, 1502, 1442 (s), 1208 (s), 1117 (s), 1079, 958, 936, 843, 799 (s), 705 (s ), 694 (s) cm ^-1 . ¹ H-NMR (400 MHz, CD ₂ Cl ₂ ): δ = 7.91-7.88 (m, 1H), 7.48-7.47 (m, 2H), 7.31 (d, ³ J = 4.2 Hz, 1H), 7.14-7.12 (m, 1H) ppm. ¹³ C-NMR (100 MHz, CD ₂ Cl ₂ ): δ = 151.6, 138.9, 136.3, 136.1, 129.3, 129.5, 128.2, 126.2 ppm. ¹⁹ F NMR (376 MHz, CD ₂ Cl ₂ ): δ = -80.67 (t, J = 9.1 Hz, 1H), -115.66--115.83 (m), -126.17 (s) ppm. (UV / Vis (CHCl ₃ ): λ _max (ε) = 384.0 nm (23300). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 447.7 nm. Fluorescence quantum yield (CHCl ₃ , λ _ex = 384.0 nm, E _{384.0 nm / 1 cm} = 0.418, standard: perylene-3,4: 9,10-tetracarboxylic acid tetramethyl ester with Φ = 1.00): 0.62 MS (70 eV, EI): m / z = 361.93 (M ⁺ ), 329.95, 193.04 (M ⁺ - C ₃ F ₇ ), 165.05 (M ⁺ - C ₄ F ₇ O), 121.11 HRMS (EI): C ₁₂ H ₆ F ₇ OS ₂ (MH ⁺ ) m / z = Ber. 362.9742, Gef 362.9746, Δ = + 0.4 mmu CHNS: calc C 39.78, H 1.39, S 17.70, C 40.49, H 1.95, S 19.04.

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1- [2,2 ': 5', 2 '' - terthiophene] -5-yl) -2,2,3,3,4,4,4-heptafluorobutan-1-one (5): In a dry glass apparatus was 2,2 ': 5', 2 '' - Terthiophen (62.8 mg, 0.250 mmol) dissolved under argon in 1.0 mL of carbon disulfide, cooled with stirring to 0 ° C, with heptafluorobutyryl chloride (0.37 mL, 581 mg, 2.50 mmol) and Aluminum chloride (83.3 mg, 0.625 mmol) was added (warm red color immediately), allowed to warm to room temperature, after 1 h and then after 2 h reaction time with additional aluminum chloride (83.3 mg, 0.625 mmol), after 3 h in a vacuum of the volatiles in vacuo, added with 5 mL of saturated ammonium chloride solution, extracted with chloroform (2 × 10 mL), evaporated with the rotary evaporator and purified by column chromatography (silica gel, iso-hexane). Y. 19.6 mg (0.0446 mmol, 18%) orange solid, mp: 107 ° C. IR (ATR): ν ~ = 1663 (s), 1500, 1449, 1433, 1344, 1228 (s), 1208 (s), 1171, 1119, 1069, 968, 938, 823, 793 (s), 787 ( s), 750, 698 (s) cm ^-1 . ¹ H-NMR (800 MHz, CD ₂ Cl ₂ ): δ = 7.90-7.89 (m, 1H), 7.40 (d, ³ J = 3.8 Hz, 1H), 7.34 (dd, ³ J = 5.1 Hz, ⁴ J = 1.1 Hz, 1H), 7.30 (d, ³ J = 4.2 Hz, 1H), 7.29 (dd, ³ J = 3.6 Hz, ⁴ J = 1.1 Hz, 1H), 7.20 (d, ³ J = 3.9 Hz, 1H ), 7.08 (dd, ³ J = 5.1 Hz, ³ J = 3.6 Hz, 1H) ppm. ¹³ C-NMR (201 MHz, CD ₂ Cl ₂ ): δ = 175.2, 150.9, 141.0, 138.7, 136.6, 135.9, 134.1, 128.7, 126.5, 125.6, 125.5 ppm. UV / Vis (CHCl ₃ ): λ _max (ε) = 432.2 nm (42200). Fluorescence (CHCl ₃ ): λ _max (I _rel ) = 528.8 nm. Fluorescence quantum eff. (CHCl ₃ , λ _Ex = 432.2 nm, E _{432.2 nm / 1 cm} = 0.470, standard: perylene-3,4: 9,10-tetracarboxylic acid tetramethyl ester with Φ = 1.00): 0.47. MS (70 eV, EI): m / z = 443.80 (M ⁺ ), 274.97 (M ⁺ - C ₃ F ₇ ), 203.01. HRMS (EI): C ₁₆ H ₇ F ₇ OS ₃ m / z = Ber. 443.9547 (M ⁺ ), Gef. 443.9539, Δ = -0.8 mmu. CHNS: Ber. C: 43.24, H: 1.59, S: 21.64, Gef C: 43.19, H: 2.27, S: 23.27.

• [1] O. Ziemann, J. Krauser, PE Zamrow, W. Daum, POF Manual. Short-range optical transmission systems, 2nd ed. Springer, Berlin 2007; ISBN 987-3-540-49093-7 ,
• [2] T. Förster, Transformation of Excitation Energy in W. Foerst (ed.), 2nd International Color Symposium: Optical Excitation of Organic Systems. Absorption and Conversion of Light Energy by Dyes and the Influences of the Medium, S. 516, Verlag Chemie GmbH, Weinheim 1966, LCCC no. 66-25750; Chem. Abstr. 1967, 67, 103925 ,
• [3] T. Förster, Fluorescence of Organic Compounds, Vandenhoeck and Ruprecht Goettingen, Götingen 1982; Chem. Abstr. 1982, 97, 162255 ,
• [4] T. Förster, Pure Appl. Chem. 1973, 34, 225-234 ,
• [5] H. Langhals, P. Knochel, T. Schlicker, C. Sämann, V. Dhayalan, Ger. Offen. DE 10 2014 003 716.9 (3/12/2014).
• [6] H. Langhals, T. Schlicker, P. Knochel, Ger. Offen. DE 10 2014 009 757.9 (6/26/2014).
• [7] G. Schopf, G. Kossmehl, Polythiophenes: Electrically Conductive Polymers, Springer, Berlin, 1997, ISBN 3-540-61483-4; ISBN 0-387-61483-4 ,
• [8th] M. Weidelener, CD Wessendorf, J. Hanisch, E. Ahlswede, G. Goetz, M. Linden, G. Schulz, E. Mena-Osteritz, A. Mishra, P. Baeuerle, Chem. Commun. 2013, 49, 10865-10867 ,
• [9] MM Khodaei, A. Alizadeh, E. Nazari, Tetrahedron Lett. 2007, 48, 4199-4202 ,
• [10] H. Wynberg, A. Logothetis, J. Am. Chem Soc. 1956, 78, 1958-1961 ,
• [11] N. Nijegorodov, R. Mabbs, Spectrochim. Acta, Part A: Molecular and Biomol. Spectroscopy 2001, 57A, 1449-1462 ,
• [12] V. Lukes, M. Danko, A. Andicsová, P. Hrdlovic, D. Végh, Synthetic Metals 2013, 165, 17-26 ,
• [13] H. Wynberg, A. Bantjes, J. Am. Chem. Soc. 1960, 82, 1447-1450 ,
• [14] MA Hempenius, BMW Langeveld-Voss, JAH van Haar, RAJ Janssen, SS Sheiko, JP Spatz, M. Moller, EW Meijer, J. Am. Chem. Soc. 1998, 120, 2798-2804 ,
• [15] M. Driver, S. Giebeler, T. Lessing, TJJ Müller, Organ. Biomol. Chem. 2013, 11 3541-3552 ,
• [16] H. Langhals, Ger. Open. DE 3016764 (30.4.980); Chem. Abstr. 1982, 96, P70417x.
• [17] Keisuke, K. Masayoshi, K. Mutsumi, ACS applied materials & interfaces 2012, 4, 6289-6294 ,
• [18] SE Koh, C. Risko, DA da Silva Filho, O. Kwon, A. Facchetti, J.-L. Bredas, TJ Marks, MA Ratner, Adv. Funct. Mater. 2008, 18, 332-340 ,
• [19] AJ Heeger, NS Sariciftci, EB Namdas, Semiconducting and Metallic Polymers, Oxford University Press, Oxford, 2010; ISBN 978-0-19-852864-7 ,
• [20] H. Dong, X. Fu, J. Liu, Z. Wang, W.Hu, Wenping, Adv. Mater. 2013, 25, 6158-6183 ,
• [21] DM DeLongchamp, RJ Kline, DA Fischer, LJ Richter, MF Toney, Adv. Mater. 2011, 23, 319-337 ,
• [22] H. Langhals, Nachr. Chem. Tech. Lab. 1980, 28, 716-718, Chem. Abstr. 1981, 95, R9816q ,
• [23] H. Langhals, J. Karolin, LB-Å. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919-2922 ,

Subject of the invention

• a. Terminal keto-functionalized oligothiophenes of the general formula 6 where n = 2 to 12,
  
  in which the radicals R ¹ to R ^{6 may be the} same or different and independently of one another the radicals R ² to R ^{5 is} hydrogen, and the radicals R ¹ to R ^{6 are} a linear alkyl radicals having at least one and at most 37 C atoms where 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 can also be replaced by a nitrogen atom, acetylenic C≡C groups 1,2-, 1,3- or 1,4-substituted phenyl radicals, 2,3-, 2,4-, 2,5-, 2,6-, 3, 4- or 3,5-disubstituted pyridine radicals, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene radicals, 1,2-, 1,3-, 1,4-, 1,5 -, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2,7-disubstituted naphthalene radicals in which one or two CH groups can be replaced by nitrogen atoms, 1, 2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2, 6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene residues in which one or two CH groups may be replaced by nitrogen atoms. Up to 40, preferably 14, individual hydrogen atoms of the CH ₂ groups may 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 having up to 18 carbon atoms in which one to 6 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 can also be replaced by a nitrogen atom , acetylenic C≡C groups, 1,2-, 1,3- or 1,4-disubstituted 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 cyano groups or linear alkyl chains having up to 18 carbon atoms, in which a to 6 CH ₂ units may be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 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 ⁸ can also independently of one another denote the halogen atoms F, Cl, Br or I.
• b. The diketoterthiophenes terminally substituted by keto groups of the general formula 7,
  
  in which the radicals R ¹ to R ^{6 have} the meaning given under a.
• c. Oligothiophenes of general formula 8 which are monosubstituted by ketoperfluoroalkyl groups terminally,
  
  where n is 1 to 7 and m is 1 to 17.
• d. The terminal ethylketo-substituted diketoterthiophenes having the formulas 1 to 4,
  
  preferably 1.
• e. A process characterized in that the diketooligothiophenes are synthesized according to a to d Friedel-Crafts acylations from the corresponding oligothiophenes and carbonyl chlorides in the typical Friedel-Crafts catalysts such as anhydrous aluminum chloride or anhydrous iron chloride, preferably alumimium chloride, and typical solvents such as carbon disulfide or Nitrobenzene, preferably carbon disulfide find Verwenung.
• f. Use of the substances according to a to d and of the 5,5 '' - diacetyl-2,2 ': 5', 2 '': 5 '', 2 '''- terthiophene as a frequency converter in optical information collecting, information processing and forwarding systems , in particular in optical light guides, preferably in fast optical systems
• G. Use of the substances according to a to d and of the 5,5 '' '- diacetyl-2,2': 5 ', 2' ': 5' ', 2' '' - terthiophene in optical slip ring systems by a light guide, z. B. a round light guide, preferably made of organic polymer material, in particular of polymethylmethacrylate (PMMA, Plexiglas), which is doped with the substances from a to c, record without any mechanical contact light, in particular modulated light from a transmitter, convert it into fluorescent light and to a recipient. The optical slip ring can be designed for rotatable systems in a round shape.
• H. Use of the substances according to a to d and terthiophene as pigments and colorants for dyeing purposes, also for decorative and artistic purposes, such as. For example, for glues and related colors such as watercolor paints and watercolors and inks for inkjet printers, paper inks, inks, inks and other colors for painting and writing and in paints, as pigments in paints, preferred paints are synthetic resin paints Acrylic or vinyl resins, polyester paints, novolaks, nitrocellulose paints (nitro lacquers) or natural products such as zapon lacquer, shellac or Qi lacquer (Japanese lacquer or Chinese lacquer or East Asian lacquer), for mass coloration of polymers, examples are materials of polyvinyl chloride , Polyvinylidene chloride, polyacrylic acid, polyacrylamide, polyvinyl butyral, polyvinyl pyridine, cellulose acetate, nitrocellulose, polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, melamine resins, silicones such as polydimethylsiloxane, polyesters, polyethers, polystyrene, polydivinylbenzene, polyvinyltoluene, polyvinylbenzylchloride, polymethylmethacrylate, polyethylene, polypropylene, polyvinylacetate , Polyacrylic itril, polyacrolein, polybutadiene, polychlorobutadiene or polyisoprene or the copolymers of said monomers, for coloring natural substances, examples are paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, Flax or its transformation products such. As the viscose fiber, nitrate silk or copper rayon (rayon), as mordant dyes, z. As for the coloring of natural products, examples include paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their conversion products such. As the viscose fiber, nitrate silk or copper rayon (rayon), preferred salts for pickling are aluminum, chromium and iron salts, as a colorant, for. As coloring of paints, lacquers and other paints, paper inks, printing inks, inks and other colors for painting and writing purposes, as an addition to other colors in which a particular shade is to be achieved, preferred are particularly bright shades.
• i. Use of the substances according to a to d and the 5,5 '' '- diacetyl-2,2': 5 ', 2' ': 5' ', 2' '' - terthiophene for marking, security and display purposes, in particular taking into account their fluorescence, such as. B. as dyes or fluorescent dyes for signal colors, preferably for the visual highlighting of logotypes and drawings or other graphic products, for marking signs and other objects and in display elements for many display, reference and marking purposes, in which a particular optical color impression can be achieved is for passive display elements, information and traffic signs, such as traffic lights for security marking purposes, the great chemical and photochemical stability and possibly also the fluorescence of the substances of importance, this is preferred for checks, check cards, banknotes, coupons, documents , Identification papers and the like, in which a special, unmistakable color impression is to be achieved, for marking objects for machine recognition of these objects via the fluorescence, preferably the machine detection of objects for sorting, z. As well as for the recycling of plastics, as fluorescent dyes for machine-readable markings, alphanumeric prints or barcodes are preferred as dyes in ink jet printers in homogeneous solution, preferably as fluorescent ink, as dyes or fluorescent dyes in display, lighting or image converter systems in which the excitation by electrons, ions or UV radiation takes place, for. As in fluorescent displays, Braun tubes or in fluorescent tubes, for tracer purposes, eg. As in biochemistry, medicine, technology and science, here, the dyes may be covalently linked to substrates or on Nebenvalenzen such as hydrogen bonds or hydrophobic interactions (adsorption), as dyes or fluorescent dyes in chemiluminescent systems, eg. As in chemiluminescent light rods, in luminescence immunoassays or other luminescence detection method and as a material for leak testing of closed systems.
• j. Use of the dyes according to a to d and of the 5,5 '''-diacetyl-2,2': 5 ', 2'':5'',2''' - terthiophene as functional materials, such. As in data storage, preferably in optical storage, such as the CD or DVD disks, in OLEDS (organic light-emitting diodes), in photovoltaic systems, as pigments in electrophotography: z. B. for dry copying systems (Xerox process) and laser printers ("Non-Impact Printing"), the frequency conversion of light, z. B. to make short-wave light of longer wavelength, visible light, as a starting material for superconducting organic materials, as fluorescent dyes in scintillators, as dyes or fluorescent dyes in optical light collection systems, such as. B. the Fluorescence solar collector or fluorescence-activated displays, in liquid crystals for deflecting light, as dyes or fluorescent dyes in cold light sources for light-induced polymerization for the preparation of plastics, as dyes or fluorescent dyes for material testing, eg. As in the manufacture and testing of semiconductor circuits and semiconductor devices, as dyes or fluorescent dyes in photoconductors, as dyes or fluorescent dyes in photographic processes, as dyes or fluorescent dyes as part of a semiconductor integrated circuit, the dyes as such or in conjunction with other semiconductors z. Example, in the form of an epitaxy, as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams, but also as a Q-switch switch and as active substances for nonlinear optics, z. B. for the frequency doubling and frequency tripling of laser light.

figure description

1 , UV / Vis spectra of 1 in chloroform. Left (dotted) absorption spectrum and right (solid) fluorescence spectrum.

2 , Fluorescence decay spectrum of 1 in chloroform in logarithmic plot. The best-fit line is completely covered by the measured values.

3 , UV / Vis spectra of 1 in PMMA. Left (dotted) fluorescence excitation spectrum and right (solid) fluorescence spectrum.

4 , Fluorescence decay spectrum of 1 in PMMA in logarithmic plot. The best-fit line is completely covered by the measured values.

5 , UV / Vis spectra of 2 in chloroform. Left (dotted) absorption spectrum and right (solid) fluorescence spectrum.

6 , Fluorescence decay spectrum of 2 in chloroform in logarithmic plot. The best-fit line is completely covered by the measured values.

7 , UV / Vis spectra of 2 in PMMA. Left (dotted) fluorescence excitation spectrum and right (solid) fluorescence spectrum.

8th , Fluorescence decay spectrum of 2 in PMMA in logarithmic plot. The best-fit line is completely covered by the measured values.

9 , UV / Vis spectra of 3 in chloroform. Left (dotted) absorption spectrum and right (solid) fluorescence spectrum.

10 , Fluorescence decay spectrum of 3 in chloroform in logarithmic plot. The best-fit line is completely covered by the measured values.

11 , UV / Vis spectra of 4 in chloroform. Left (dotted) absorption spectrum and right (solid) fluorescence spectrum.

12 , Fluorescence decay spectrum of 4 in chloroform in logarithmic plot. The best-fit line is completely covered by the measured values.

13 , UV / Vis spectra of 5 in chloroform. Left (dotted) absorption spectrum and right (solid) fluorescence spectrum.

14 , Fluorescence decay spectrum of 5 in chloroform in logarithmic plot. The best-fit line is completely covered by the measured values.

15 , UV / Vis spectra of 5 in PMMA. Left (dotted) fluorescence excitation spectrum and right (solid) fluorescence spectrum.

16 , Fluorescence decay spectrum of 5 in PMMA in logarithmic plot. The best-fit line is completely covered by the measured values.

QUOTES INCLUDE IN THE DESCRIPTION

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

Cited patent literature

• DE 102014003716 [0019]
• DE 102014009757 [0019]
• DE 3016764 [0019]

Cited non-patent literature

• O. Ziemann, J. Krauser, PE Zamrow, W. Daum, POF Manual. Short-range optical transmission systems, 2nd ed. Springer, Berlin 2007; ISBN 987-3-540-49093-7 [0019]
• T. Förster, Transformation of Excitation Energy in W. Foerst (ed.), 2nd International Color Symposium: Optical Excitation of Organic Systems. Absorption and Conversion of Light Energy by Dyes and the Influences of the Medium, S. 516, Verlag Chemie GmbH, Weinheim 1966, LCCC no. 66-25750; Chem. Abstr. 1967, 67, 103925 [0019]
• T. Förster, Fluorescence of Organic Compounds, Vandenhoeck and Ruprecht Goettingen, Götingen 1982; Chem. Abstr. 1982, 97, 162255 [0019]
• T. Förster, Pure Appl. Chem. 1973, 34, 225-234 [0019]
• G. Schopf, G. Kossmehl, Polythiophenes: Electrically Conductive Polymers, Springer, Berlin, 1997, ISBN 3-540-61483-4; ISBN 0-387-61483-4 [0019]
• M. Weidelener, CD Wessendorf, J. Hanisch, E. Ahlswede, G. Goetz, M. Linden, G. Schulz, E. Mena-Osteritz, A. Mishra, P. Baeuerle, Chem. Commun. 2013, 49, 10865-10867 [0019]
• MM Khodaei, A. Alizadeh, E. Nazari, Tetrahedron Lett. 2007, 48, 4199-4202 [0019]
• H. Wynberg, A. Logothetis, J. Am. Chem Soc. 1956, 78, 1958-1961 [0019]
• N. Nijegorodov, R. Mabbs, Spectrochim. Acta, Part A: Molecular and Biomol. Spectroscopy 2001, 57A, 1449-1462 [0019]
• V. Lukes, M. Danko, A. Andicsová, P. Hrdlovic, D. Vegh, Synthetic Metals 2013, 165, 17-26 [0019]
• H. Wynberg, A. Bantjes, J. Am. Chem. Soc. 1960, 82, 1447-1450 [0019]
• MA Hempenius, BMW Langeveld-Voss, JAH van Haar, RAJ Janssen, SS Sheiko, JP Spatz, M. Moller, EW Meijer, J. Am. Chem. Soc. 1998, 120, 2798-2804 [0019]
• M. Driver, S. Giebeler, T. Lessing, TJJ Müller, Organ. Biomol. Chem. 2013, 11 3541-3552 [0019]
• T. Keisuke, K. Masayoshi, K. Mutsumi, ACS applied materials & interfaces 2012, 4, 6289-6294 [0019]
• SE Koh, C. Risko, DA da Silva Filho, O. Kwon, A. Facchetti, J.-L. Bredas, TJ Marks, MA Ratner, Adv. Funct. Mater. 2008, 18, 332-340 [0019]
• AJ Heeger, NS Sariciftci, EB Namdas, Semiconducting and Metallic Polymers, Oxford University Press, Oxford, 2010; ISBN 978-0-19-852864-7 [0019]
• H. Dong, X. Fu, J. Liu, Z. Wang, W.Hu, Wenping, Adv. Mater. 2013, 25, 6158-6183 [0019]
• DM DeLongchamp, RJ Kline, DA Fischer, LJ Richter, MF Toney, Adv. Mater. 2011, 23, 319-337 [0019]
• H. Langhals, Nachr. Chem. Tech. Lab. 1980, 28, 716-718, Chem. Abstr. 1981, 95, R9816q [0019]
• H. Langhals, J. Karolin, LB-Å. Johansson, J. Chem. Soc., Faraday Trans. 1998, 94, 2919-2922 [0019]

Claims (10)

Terminal keto-functionalized oligothiophenes of the general formula 6 where n = 2 to 12,

in which the radicals R ¹ to R ^{6 may be the} same or different and independently of one another the radicals R ² to R ^{5 is} hydrogen, and the radicals R ¹ to R ^{6 are} a linear alkyl radicals having at least one and at most 37 C atoms where 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 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 can be replaced by nitrogen atoms, 1,2-, 1, 3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2, 7-, 2,9-, 2,10- or 9,10-disub substituted anthracene residues in which one or two CH groups can be replaced by nitrogen atoms. Up to 40, preferably 14, individual hydrogen atoms of the CH ₂ groups may 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 having up to 18 carbon atoms in which one to 6 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 can also be replaced by a nitrogen atom , acetylenic C≡C groups, 1,2-, 1,3- or 1,4-disubstituted 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 cyano groups or linear alkyl chains having up to 18 carbon atoms, in which a to 6 CH ₂ units may be replaced independently by carbonyl groups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis or trans-CH = CH groups in which a CH unit may also be replaced by a nitrogen atom, acetylenic C≡ C groups, 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 ⁸ can also independently of one another denote the halogen atoms F, Cl, Br or I. The diketoterthiophenes terminally substituted by keto groups of the general formula 7,

in which the radicals R ¹ to R ^{6 have} the meaning given under a. Oligothiophenes of general formula 8 which are monosubstituted by ketoperfluoroalkyl groups terminally,

where n is 1 to 7 and m is 1 to 17. The terminal ethylketo-substituted diketoterthiophenes having the formulas 1 to 4,

preferably 1. A process characterized in that the diketooligothiophenes are synthesized according to a to d Friedel-Crafts acylations from the corresponding oligothiophenes and carbonyl chlorides in the typical Friedel-Crafts catalysts such as anhydrous aluminum chloride or anhydrous iron chloride, preferably alumimium chloride, and typical solvents such as carbon disulfide or Nitrobenzene, preferably carbon disulfide find Verwenung. Use of the substances according to a to d and of the 5,5 '' '- diacetyl-2,2': 5 ', 2' ': 5' ', 2' '' - terthiophene as a frequency converter in optical information collecting, information processing and Forwarding systems, especially in optical light guides, preferably in fast optical systems Use of the substances according to a to d and of the 5,5 '' '- diacetyl-2,2': 5 ', 2' ': 5' ', 2' '' - terthiophene in optical slip ring systems by a light guide, z. B. a round light guide, preferably made of organic polymer material, in particular of polymethylmethacrylate (PMMA, Plexiglas), which is doped with the substances from a to c, record without any mechanical contact light, in particular modulated light from a transmitter, convert it into fluorescent light and to a recipient. The optical slip ring can be designed for rotatable systems in a round shape. Use of the substances according to a to d and of the 5,5 '''-diacetyl-2,2': 5 ', 2'':5'',2''' - terthiophene as pigments and colorants for dyeing purposes, also for decorative purposes and artistic purposes, such as B. for glues and related colors such as watercolor paints and watercolors and colors for inkjet printers, paper inks, inks, inks and inks and other colors for painting and writing purposes and in Paints, as pigments in paints, preferred paints are synthetic resin paints such as acrylic or vinyl resins, polyester paints, novolaks, nitrocellulose paints (nitro lacquers) or natural products such as zapon lacquer, shellac or qi lacquer (Japanese lacquer or Chinese lacquer or East Asian lacquer) for bulk dyeing of polymers, examples are materials of polyvinyl chloride, polyvinylidene chloride, polyacrylic acid, polyacrylamide, polyvinylbutyral, polyvinylpyridine, cellulose acetate, nitrocellulose, polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, melamine resins, silicones such as polydimethylsiloxane, polyesters, polyethers, polystyrene, Polydivinylbenzene, polyvinyltoluene, polyvinylbenzyl chloride, polymethyl methacrylate, polyethylene, polypropylene, polyvinyl acetate, polyacrylonitrile, polyacrolein, polybutadiene, polychlorobutadiene or polyisoprene or the copolymers of said monomers, for coloring natural products, examples are paper, wood, straw, or natural fiber material n such as wool, hair, pet hair, bristles, cotton, jute, sisal, hemp, flax or their conversion products such. As the viscose fiber, nitrate silk or copper rayon (rayon), as mordant dyes, z. As for the coloring of natural products, examples include paper, wood, straw, or natural fiber materials such as wool, hair, animal hair, bristles, cotton, jute, sisal, hemp, flax or their conversion products such. As the viscose fiber, nitrate silk or copper rayon (rayon), preferred salts for pickling are aluminum, chromium and iron salts, as a colorant, for. As coloring of paints, lacquers and other paints, paper inks, printing inks, inks and other colors for painting and writing purposes, as an addition to other colors in which a particular shade is to be achieved, preferred are particularly bright shades. Use of the substances according to a to d and the 5,5 '' '- diacetyl-2,2': 5 ', 2' ': 5' ', 2' '' - terthiophene for marking, security and display purposes, in particular taking into account their fluorescence, such as. B. as dyes or fluorescent dyes for signal colors, preferably for the visual highlighting of logotypes and drawings or other graphic products, for marking signs and other objects and in display elements for many display, reference and marking purposes, in which a particular optical color impression can be achieved is for passive display elements, information and traffic signs, such as traffic lights for security marking purposes, the great chemical and photochemical stability and possibly also the fluorescence of the substances of importance, this is preferred for checks, check cards, banknotes, coupons, documents , Identification papers and the like, in which a special, unmistakable color impression is to be achieved, for marking objects for machine recognition of these objects via the fluorescence, preferably the machine detection of objects for sorting, z. As well as for the recycling of plastics, as fluorescent dyes for machine-readable markings, alphanumeric prints or barcodes are preferred as dyes in ink jet printers in homogeneous solution, preferably as fluorescent ink, as dyes or fluorescent dyes in display, lighting or image converter systems in which the excitation by electrons, ions or UV radiation takes place, for. As in fluorescent displays, shower tubes or in fluorescent tubes, for tracer purposes, eg. As in biochemistry, medicine, technology and science, here, the dyes may be covalently linked to substrates or on Nebenvalenzen such as hydrogen bonds or hydrophobic interactions (adsorption), as dyes or fluorescent dyes in chemiluminescent systems, eg. As in chemiluminescent light rods, in luminescence immunoassays or other luminescence detection method and as a material for leak testing of closed systems. Use of the dyes according to a to d and of the 5,5 '' '- diacetyl-2,2': 5 ', 2' ': 5' ', 2' '' - terthiophene as functional materials, such. As in data storage, preferably in optical storage, such as the CD or DVD disks, in OLEDS (organic light-emitting diodes), in photovoltaic systems, as pigments in electrophotography: z. B. for dry copying systems (Xerox process) and laser printers ("Non-Impact Printing"), the frequency conversion of light, z. B. to make short-wave light of longer wavelength, visible light, as a starting material for superconducting organic materials, as fluorescent dyes in scintillators, as dyes or fluorescent dyes in optical light collection systems, such as. As the fluorescent solar collector or fluorescence-activated displays, in liquid crystals for deflecting light, as dyes or fluorescent dyes in cold light sources for light-induced polymerization for the preparation of plastics, as dyes or fluorescent dyes for material testing, eg. As in the manufacture and testing of semiconductor circuits and semiconductor devices, as dyes or fluorescent dyes in photoconductors, as dyes or fluorescent dyes in photographic processes, as dyes or fluorescent dyes as part of a semiconductor integrated circuit, the dyes as such or in conjunction with other semiconductors z. Example, in the form of an epitaxy, as dyes or fluorescent dyes in dye lasers, preferably as fluorescent dyes for generating laser beams, but also as a Q-switch switch and as active substances for nonlinear optics, z. B. for the frequency doubling and frequency tripling of laser light.

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