WO2015135867A1

WO2015135867A1 - Terminal substituted oligothiophenes and use thereof in optical signal transmission systems and/or as colour pigments

Info

Publication number: WO2015135867A1
Application number: PCT/EP2015/054805
Authority: WO
Inventors: Heinz Langhals; Paul Knochel; Thorben SCHLÜCKER; Christoph SÄMANN; Dhayalan VASUDEVAN
Original assignee: Ludwig-Maximilians-Universität München
Priority date: 2014-03-12
Filing date: 2015-03-09
Publication date: 2015-09-17
Also published as: DE112015001170A5

Abstract

The invention relates to oxidation-stable oligothiophenes of formula (I), with one or two terminal substitutes, which are respectively bound to the oligothiophene chain by means of a quaternary carbon atom. Based on the characteristic absorption and fluorescence properties thereof, such as a large stroke shift, and based on the good controllable solubility thereof, the claimed compounds are suitable, in particular, for use in optical signal transmission systems which allow high data transmission rates, and/or as colouring agents.

Description

TERMINAL SUBSTITUTED OLIGOTHIOPHENE AND ITS USE IN

OPTICAL SIGNAL TRANSMISSION SYSTEMS AND / OR AS COLOR PIGMENTS

The invention relates to oxidation-stable, terminally substituted oligothiophenes which, owing to their characteristic absorption and fluorescence properties and owing to their readily controllable solubility, are particularly suitable for use in optical signal transmission systems and / or as colorants.

Digital information transfer is becoming increasingly important. To cope with the increasing volume of information, ever faster data transmission systems are needed. At present, interest is increasingly turning to optical signal transmission links, which in principle allow extraordinarily high transmission rates to be achieved, for example in Internet transcontinental cables. While the optical data transmission between stationary systems with lines is well developed (O. Zimmermann, J. Krauser, PE Zamrow, W. Daum, POF manual, optical short-distance transmission systems, 2nd edition Springer, Berlin 2007), prepares the data transmission between moving parts still technical problems. If these parts perform periodic movements, one can resort to flexible systems, which are then heavily loaded with mechanical stress. In completely separate parts of this method is no longer applicable, and it must be called slip ring systems, also referred to as a rotary transfer device. However, electrical slip ring systems are severely limited in terms of transmission frequency because the required mechanics adversely affect the electrical properties. While this can still be tolerated at low frequencies, the problem becomes increasingly serious at higher frequencies. In contrast, optical transmission systems are considerably more attractive. However, purely geometrical optics place considerable demands on the mechanical and optical precision, in particular because with fully rotatable components light from all directions must reliably hit the receiver. Fluorescent light harvesting systems, known, for example, as fluorescence solar collectors (H.Langhals, Nachr. Chem. Tech .Lab., 1980, 28, 716-718, Chem. Abstr., 1981, 95, R9816q), are particularly attractive here; They consist of a light guide made of a transparent material, such as Plexiglas (polymethyl methacrylate), which is homogeneously colored with a fluorescent dye. In such systems, light from all spatial directions can penetrate into the light guide with refraction of light, is absorbed by the fluorescent dye dissolved there and isotropic in all Spaces emitted as fluorescent light again. Of the fluorescent light, however, only a small part of the light guide leave again, namely the light that hits steeply on the optical fiber surface, while the main part that hits flat on the surface, is reflected by total reflection in the light guide and concentrated at the end surfaces again can be removed. In the case of optical slip ring systems, it would be preferable to use annular, circular light guides which can pick up light from all positions and then release it in a concentrated manner via the fluorescence at the end faces. The system is suitable for contactless transmission of information in a completely rotatable arrangement of the components. However, it is limited by the fluorescence decay time of the fluorescent dye, which is usually about 5 ns in the case of strongly fluorescent dyes (T. Förster, Transformation of Excitation Energy in W. Foerst (ed.), 2nd International Color Symposium: Optical Excitation of Organic Systems 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). According to a theory by Förster (T. Förster, Fluorescence Organic Compounds, Vandenhoeck and Ruprecht Goettingen, Gottingen 1982; Chem. Abstr., 1982, 97, 162255; T. Forster, Pure Appl. Chem., 1973, 34, 225-234) Fluorescence quantum yields, molar extinction coefficients. and fluorescence decay times by giving the fluorescence decay time for highly fluorescent substances by the natural transition probability of the particular electron transition reflected by the extinction coefficient. For strongly fluorescent substances, such as perylene dyes, with high molar extinction coefficients of 100 000 L-mof 'cm ^"1 , the approximately 5 ns fluorescence decay time results from the natural probability of electron transfer If the available luminous efficacy leads to an appreciable increase in the extinction coefficient, shortening the fluorescence decay time in the case of strongly fluorescent chromophores is less promising, but would mean a considerable (local step in non-contact signal transmission.

Oligothiophene (eg G. Schopf, G. Kossmehl, Polythiophenes: Electrically Conduc ve Polymers, Springer, Berlin, 1997: 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) find a variety of applications in material science (T.Keisuke, K. Masayoshi, K. Mutsumi, ACS applied materials & Interfaces 2012, 4, 6289-6294: p. E.Koh, C. Risko, DA da Silva Filho, O. Kwon, A. Facchetti, J.-L. Bredas, TJMarks, MA Ratner, Adv. Funct. Mater. 2008, 18, 332-340; AJ Heeger, NS Sariciftci, EB Namdas, Semiconducut and Metallic Polymers, Oxford University Press, Oxford, 2010). However, these substances are relatively poorly soluble and therefore less suitable for homogeneous solution or polymer matrix applications (Dong, Dong, Fu, J. Liu, Z. Wang, W. Hu, Wenping, Adv, Mater., 2013, 25 , DeLongchamp, RJ Kline, DA Fischer, LJ Richter, MF Toney, Adv. Mater., 2011, 23, 319-337), 6158-6183; Although 3,4-dialkylthiophenes having better solubility are known. However, it has proved to be disadvantageous that these substances are less stable to oxidation, which makes their use difficult.

The object of the present invention was therefore to provide stable compounds having readily controllable solubility properties which have suitable absorption or fluorescence properties and in particular exhibit short fluorescence decay times.

The invention provides terminally substituted oligothiophenes of the formula (I) for this purpose:

wherein the variables Rl to R6 and n are defined as follows.

R 1, R 2 and R 3 are each independently selected from an alkyl radical, an alkenyl radical and an aryl radical which may be substituted by one or more substituents RIO,

wherein two radicals selected from R 1, R 2 and R 3, each independently representing an alkyl radical or an alkenyl radical, together with the carbon to which they are attached may be linked to a cycloalkane radical or a cycloalkene radical which may be substituted by one or more Substituents RI O, or all three of the radicals Rl, R2 and R3, each independently an alkyl radical or an alkenyl radical, together with the Carbon to which they are attached may be linked to a bridged cycloalkane or bridged cycloalkene radical which may be substituted with one or more substituents RIO.

R6 is selected from H and a radical -C (R1R2R3) wherein R1, R2 and R3 are as defined above, n represents an integer from 2 to 12.

R4 and R5 are each independently selected from hydrogen, F, Cl, Br, I and a linear alkyl group having at least one and at most 37 C atoms, wherein in the alkyl group, one to 10 CH ₂ units may be independently replaced in each case by a carbonyl group, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, an iron or trach-CH =CH group in which a CH unit can also be replaced by a nitrogen atom, an acetylenic C 1 -C 4 Group, a divalent phenyl radical, a divalent pyridine radical, a divalent thiophene radical, a divalent naphthalene radical in which one or two CH groups may be replaced by nitrogen atoms, a divalent anthracene radical in which one or two CH groups may be replaced by nitrogen atoms ; and wherein in the alkyl radical up to 12 individual hydrogen atoms of the CH ₂ groups may each be independently replaced by the same carbon atoms by a halogen, a cyano group or a linear alkyl chain having up to 18 carbon atoms, in which a bis 6 CH ₂ - units can be replaced independently of each other by a carbonyl group, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, an eis or / r <mv-CH = CH- G nippe, in which a CH unit also may be replaced by a nitrogen atom, an acetylenic C = C group, a divalent phenyl radical, a divalent pyridine radical, a divalent thiophene radical, a divalent naphthalene radical in which one or two CH groups may be replaced by nitrogen atoms, a divalent anthracene radical. in which one or two CH groups may be replaced by nitrogen atoms, and w ^r obei up to 12 single hydrogen atoms of the CH ₂ groups of the alkyl chain may be replaced each independently of one another and on the same C-atoms by a halogen, a cyano group or a linear alkyl chain containing up to 18 carbon atoms, in which one to 6 CFb units can be replaced independently of each other by a carbonyl group, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, a cis- or racemate "-CH = CH group in which a CH unit may also be replaced by a nitrogen atom, an acetylenic C = C group, a divalent phenyl radical, a divalent pyridine radical, a divalent thiophene radical, a divalent naphthalene radical in which one or two CH groups may be replaced by nitrogen atoms, a divalent anthracene radical in which one or two CH groups may be replaced by nitrogen atoms;

and wherein the free valencies of methine groups or of quaternary C atoms in such alkyl radicals can also be linked in pairs, so that a ring is formed.

The optional substituents R 1 O to R 1, R 2 and / or R 3 are independently selected from F, Cl, Br, I and a linear alkyl radical as defined above for R 4 and R 5.

Further aspects of the invention relate to processes for preparing such compounds, polymer compositions in which the compounds are dispersed in a polymer matrix or form a copolymer together with the polymer of the polymer matrix, and light-conducting materials, in particular optical slip rings, in which the compounds according to the invention or the polymer compositions be used.

As explained above, the terminal substituted oligothiophenes of the present invention which can carry one or two terminal substituents have a structure represented by the following formula (1):

and wherein the variables R1 to R6 and n are defined as follows.

Rl. R 2 and R 3 are each independently selected from an alkyl radical, an alkene radical and an aryl radical which may be substituted with one or more substituents R 1 O. wherein two radicals selected from R 1, R 2 and R 3 are each independently an alkyl radical or an alkenyl radical represent, together with the carbon to which they are attached, to be linked to a cycloalkane radical or a cycloalkene radical which may be substituted by one or more substituents RI O, or all three of the radicals Rl, R2 and R3, each independently an alkyl radical or an Alkenvlrest, together with the carbon to which they are attached may be linked to a bridged cycloalkene radical or bridged cycloalkane radical which may be substituted by one or more substituents RIO.

Preferably, the radicals Rl. R 2 and R 3 are each independently selected from an alkyl radical and an alkenyl radical wherein the three radicals R 1, R 2 and R 3 together with the carbon to which they are attached are linked to a bridged cycloalkane radical or a bridged cycloalkene radical which may be substituted with one More preferably, the three radicals R 1, R 2 and R 3 together with the carbon to which they are attached form a bridged cycloalkane radical which may be substituted with one or more substituents R 10, and more preferably form an unsubstituted one bridged cycloalkane.

If one of the radicals R 1, R 2 or R 3 is an alkoxy radical, this preferably has 1 to 12, more preferably 2 to 8, carbon atoms. If one of the radicals R 1, ^R 2 or R 3 is an alkenyl radical, this is preferably from 2 to 12, more preferably from 2 to 8, carbon atoms. The alkyl radicals and alkenyl radicals can be linear or branched. Is one of the radicals Rl. R2 or R3 is an aryl radical, this preferably has 6 or 10 carbon atoms, more preferably 6 carbon atoms. Each radical R 1, R 2 and R 3 preferably carries at most one substituent R 10, particularly preferably the radicals R 1, R 2 and R 3 carry no substituent R 10. If two radicals are selected from R 1, R 2 and R 3, which each independently represent an alkyl radical or an alkenyl radical, together with the carbon to which they are attached, linked to a cycloalkane radical or a cycloalkene radical, this cycloalkane radical or cycloalkene radical preferably has 5 to 12 carbon atoms. Such a cycloalkane radical or cycloalkene radical is preferably unsubstituted. Are all three of the radicals Rl. R 2 and R 3, which are each independently an alkyl radical or an alkenyl radical, together with the carbon to which they are attached, link to a bridged cycloalkene radical or linked cycloalkane radical, this bridged cycloalkene radical or bridged cycloalkane radical preferably has from 6 to 12, particularly preferably 8 up to 10 carbon atoms. Such a bridged cycloalkane radical or bridged cycloalkene radical is preferably unsubstituted.

Particularly suitable radicals -C (R 1 R 2 R 3) are bridged cycloalkane radicals in which the three radicals R 1, R 2 and R 3 are joined together with the carbon to which they are attached and which are selected from a 1-adamantane radical, 1- or 3 Homoadamantane radical, 1- β-bicyclo [2.2.2] octane radical, 1-bicyclo [3.3.1 ionone radical, 1-bicyclo [3.2.2] nonane radical,

Bicyclo [3.3.2] decane residue, 1 -twistric residue and a 1-norbornyl residue. These radicals may be substituted with one or more substituents RIO, but are preferably unsubstituted. As can be seen from the formula (I), the bridged cycloalkane moiety is linked to the thiophene group through a bridgehead atom, that is, an atom which would exist as the tertiary carbon atom in the bridged cycloalkane not yet connected to the thiophene. Especially preferred as the bridged cycloalkane radical is the adamantane radical which is bonded to the thiophene group as a 1-adamantane radical. This radical may also be substituted by one or more substituents RIO, but is preferably unsubstituted.

R6 is selected from H and a radical -C (R1R2R3). ie a radical of the formula (i)

wherein R 1, R 2 and R 3 are independently as defined above, including the preferred definitions. n represents an integer from 2 to 12, preferably from 2 to 8.

For single terminally substituted compounds of formula (I) (i.e., where R6 = H), values of from 2 to 6 are more preferred for n, and even more preferred are values of from 2 to 4. Particularly preferred is n = 3 or 4.

In the case of terminally disubstituted compounds of the formula (I) (ie where R 6 = -C (R 1 R 2 R 3)) n is more preferably 4 to 8. Because of convenient accessibility, as discussed below, for terminally disubstituted compounds of the formula (I) (ie R 6 = -C (R 1 R 2 R 3)) even values within the abovementioned ranges and preferred ranges are again preferred, ie 2, 4, 6, 8, 10 and 12 or 4, 6. 8. 10 and 12, in particular 4. 6 and 8.

R4 and R5 are independently selected at each occurrence from hydrogen, F, CS. Br, 1 and a linear alkyl group having at least one and at most 37 C atoms, wherein in the alkyl group, one to 10 CH ₂ units may be independently replaced each with a carbonyl group, an oxygen atom, a sulfur atom, a selenium atom Tellurium atom, an egg or

in which a CH unit may also be replaced by a nitrogen atom, an acetylenic C = C group, a divalent phenyl radical (for example a 1,2-, 1, 3 or 1,4-phenyl radical), a divalent pyridine radical (eg a 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-pyridine radical), a divalent thiophene radical (eg a 2,3-, 2,4-, 2 , 5- or 3,4-thiophene radical), a divalent naphthalene radical (eg a 1,2-, 1, 3, 1, 4, 1, 5, 1, 6, 1, 7, 1, 8 -, 2,3-, 2,6- or 2,7-naphthalene) in which one or two CH groups may be replaced by nitrogen atoms, a divalent anthracene (eg a 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-anthracene radical) in which one or two CH groups may be replaced by nitrogen atoms;

and wherein in the alkyl radical up to 12 individual hydrogen atoms of the Cffe-Grappen can each be independently replaced by the same C-atoms by a halogen (fluorine, chlorine, bromine or iodine), a cyano group or a linear Aikylkette up to 18 C. - atoms in which one to 6 CI T units can be replaced independently of each other by a carbonyl group, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, an eis or a-CH = CH group in which a CH Unit may also be replaced by a nitrogen atom, an acetylenic C =C group, a divalent phenyl radical (eg a 1,2-, 1,3- or 1,4-phenyl radical), a divalent pyridine radical (eg a 2, 3, 2,4, 2,5, 2,6, 3,4 or 3, 5-pyridine). a divalent thiophene radical (eg a 2,3-, 2,4-, 2,5- or 3,4-thiophene radical), a divalent naphthalene radical (eg a 1,2-, 1, 3-, 1, 4-, 1.5-, 1.6-, 1.7-, 1, 8-, 2,3-, 2,6- or 2,7-naphthalene radical) in which one or two CH groups may be replaced by nitrogen atoms, a divalent anthracene radical (for example a 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 anthracene residue) in which one or two CH groups may be replaced by nitrogen atoms and wherein up to 12 individual Wasserloffatome the CHV groups of the Aikylkette each be replaced independently of the same C atoms may be replaced by a halogen (fluorine, chlorine, bromine or iodine), a cyano group or a linear Aikylkette having up to 18 carbon atoms, in which one to 6 CI Ii units may be replaced independently by a carbonyl group, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, an ice or tram CH = C H group in which a CH unit may also be replaced by a nitrogen atom, an acetylenic C = C group, a divalent phenyl radical (eg a 1, 2, 1, 3 or 1, 4 phenyl radical), a divalent pyridine radical (eg a 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-pyridine resf), a divalent thiophene radical (eg a 2,3-, 2,4- , 2,5- or 3,4-thiophene radical), a divalent naphthalene radical (eg a 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, 1.7, 1, 8 , 2,3-, 2,6- or 2,7-naphthalene radical) in which one or two CH groups have been replaced by nitrogen atoms can, a divalent Antliracenrest (for example, a 1,2-, 1,3-, 1, 4, 3, 5, 1, 6, 1.7, 1, 8, 1, 9, 1, 10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-antiracea residue) in which one or two CH groups may be replaced by nitrogen atoms,

and wherein the free valencies of methine groups or of quaternary C atoms in alkyl radicals can also be linked in pairs, so that a ring is formed, such as a ring. a cyclohexane ring.

As will be understood by those skilled in the art, in the context of this specification, a CHb moiety of an alkyl group or an alkyl chain which can be substituted by definition also may be a terminal moiety in an alkyl group / chain, i. a corresponding formal CHi unit within a -CEE, group act. Accordingly, this applies to the methine groups, which can be linked in pairs, so that rings arise. These methine groups may also each be a formal CH moiety present within a CH ^ group or a CEfr group and additionally having a free valence to form a ring having a second corresponding group. The quaternary C atoms. which may be linked in pairs, may result when in a CIE group a monovalent substituent has already replaced a hydrogen atom and, in addition, a free valence to form a ring with a second corresponding group is present.

Preferably, R4 and R5 independently of each occurrence are selected from hydrogen, F, and a linear alkyl radical having at least one and at most 37 C atoms, wherein in the alkyl radical one to 10 CHi units can be replaced independently of one another by an ice or trans-CH ^ CH group in which a CH unit may also be replaced by a nitrogen atom, an acetylenic C ^ C group, a divalent phenyl radical, a divalent pyridine radical, a divalent thiophene radical. a divalent naphthalene radical in which one or two CH groups may be replaced by nitrogen atoms, a divalent Antliracenrest in which one or two CH groups may be replaced by nitrogen atoms; and wherein in the alkyl radical up to 12 individual W ^T ererstoffatome the Cl E groups can each be independently replaced by the same carbon atoms by a linear alkyl chain having up to 18 carbon atoms, in which one to 6 C! Ii units can be replaced independently of one another by in each case one cis or trans Cli = Cll group, in which a CH unit can also be replaced by a nitrogen atom, an acetylenic C 1 -C 4 group, a divalent phenyl radical, a divalent one Pyridine radical, a divalent thiophene radical, a divalent naphthalene radical in which one or two CH groups are replaced by nitrogen atoms may be a divalent anthracene radical in which one or two CH groups may be replaced by nitrogen atoms and wherein up to 12 individual hydrogen atoms of the CH ₂ - groups of the alkyl chain may each be replaced independently of the same carbon atoms by a linear alkyl chain with up to 18 carbon atoms, in which one to 6 CH ₂ units can be replaced independently of each other by a respective cis or tram-CH ^ CH group in which a CH unit can also be replaced by a nitrogen atom, a acetylenic C-μC group. a divalent phenyl radical, a divalent pyridine radical, a divalent thiophene radical, a divalent naphthalene radical in which one or two CH groups may be replaced by nitrogen atoms, a divalent anthracene radical in which one or two CH groups may be replaced by nitrogen atoms;

More preferably, R4 and R5 independently of each occurrence are selected from hydrogen, F. and a linear alkyl group having at least one and at most 37 C atoms. Most preferably, R4 and R5 are hydrogen.

The optional substituents R 1 O to R 1, R 2 and / or R 3 are independently selected from F, Cl, Br, I and a linear alkyl radical having at least one and at most 37 C atoms,

wherein in the alkyl group, one to 10 CI F units may be independently replaced by each of a carbonyl group, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, a cis- or / ram'-CH = CH group in which one CH unit may also be replaced by a nitrogen atom, an acetylenic OC group, a divalent phenyl radical (eg a 1,2-, 1, 3- or 1,4-phenyl radical), a divalent pyridine radical (eg a 2,3-, 2 , 4-, 2,5-, 2,6-, 3,4- or 3,5-pyridine radical), a divalent thiophene radical (eg a 2,3-, 2,4-, 2,5- or 3,4-thiophene radical ), a divalent naphthalene radical (eg a 1, 2, 1.3, 1.4, 1, 5, 1.6, 1.7, 1, 8, 2,3, 2,6 or 2 , 7-naphthalene radical) in which one or two CH groups may be replaced by nitrogen atoms, a divalent anthracene radical (eg a 1, 2-1, 3-, 1, 4-, L5-, 1,6-, 1 , 7, 1, 8, 1, 9, 1, 10, 23, 2,6, 2,7, 2, 9, 2, 10 or 9, 10 anthracene residue) the one or two CH groups through Sticksto ffatome can be replaced;

and wherein in the alkyl radical up to 12 individual hydrogen atoms of the Cl F groups can each independently be replaced by the same C atoms by a halogen (fluorine, chlorine, bromine or iodine). a cyano group or a linear alkyl chain with up to 1 8 C Atoms in which one to six CIT units can be replaced independently of each other by a carbonyl group, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, an ice or

in which a CH unit may also be replaced by a nitrogen atom, an acetylenic C = C group, a divalent phenyl radical (eg a 1, 2, 1, 3 or 1, 4-phenyl radical), a divalent pyridine radical (eg a 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-pyridine radical), a divalent thiophene radical (eg a 2,3-, 2,4-, 2,5- or 3, 4-thiophene radical), a divalent naphthalene radical (eg a 1,2-, 1, 3, i, 4, 1, 5, 1, 6, 1.7, 1.8, 2.3, 2.6 - or 2.7-Naphthalinrest) in which one or two CH groups may be replaced by nitrogen atoms, a divalent anthracene radical (eg, a 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 anthracene in which one or two CH groups can be replaced by nitrogen atoms and wherein up to 12 individual hydrogen atoms of the CIE groups of the alkyl chain can each independently be replaced by the same C atoms by a halogen (fluorine, chlorine, bromine or Iodine), a C yano group or a linear alkyl chain having up to 18 carbon atoms, in which one to 6 CH? units can be replaced independently of one another by a carbonyl group, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, an cis- or trans- CH = CH group in which a CH unit can also be replaced by a nitrogen atom, an acetylenic C 1 -C 4 group, a divalent phenyl radical (eg a 1,2-, 1, 3 or 1, 4-phenyl radical) , a divalent pyridine radical (eg a 2.3-. 2,4-, 2,5-, 2,6-, 3,4- or 3,5-pyridine radical), a divalent thiophene radical (eg a 2,3-, 2,4-, 2,5- or 3,4-thiophene radical). a divalent naphthalene radical (eg a 1, 2, 1, 3, 1.4, 1, 5, 1, 6, 1.7, 1.8, 2.3, 2.6 or 2.7 naphthalene radical) in which one or two CH groups may be replaced by nitrogen atoms, a divalent anthracene residue (eg a 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-anthracene). in which one or two CH groups may be replaced by nitrogen atoms;

and wherein the free radicals of methine groups or of quaternary C atoms in alkyl radicals can also be linked in pairs so that a ring is formed, such as, for example, a cyelohexane ring.

The optional substituents R.sup.1O, R.sup.2 and / or R.sup.3 are preferably selected independently of one another from F and a linear alkyl radical having at least one and at most 37 C atoms,

where in the alkyl radical one to 10 C T-kynheiten can be replaced independently of each other by an ice - or iransl 1 = C11 group in which a CH unit can also be replaced by a nitrogen atom, an acetylenic C = C. -Group. a divalent phenyl radical. a divalent pyridine radical, a divalent thiophene radical, a divalent naphthalene radical in which one or two CH groups may be replaced by nitrogen atoms, a divalent anthracene radical in which one or two CH groups may be replaced by nitrogen atoms; and wherein in the alkyl radical up to 12 individual hydrogen atoms of the CH? groups may each be independently replaced on the same carbon atoms by a linear alkyl chain having up to 18 carbon atoms, in which one to 6 CH ₂ units independently can be replaced by one each ice or

in which a CH unit may also be replaced by a nitrogen atom, an acetylenic C = C group, a divalent phenyl radical, a divalent pyridine radical, a divalent thiophene radical, a divalent naphthalene radical in which one or two CH groups have been replaced by nitrogen atoms can, a divalent anthracene residue. in which one or two CH groups can be replaced by nitrogen atoms and wherein up to 12 individual hydrogen atoms of the ^(' !) groups of the alkyl chain can each independently be replaced by identical C atoms by a linear alkyl chain with up to 18 C atoms, in which one to 6 CHi units can be replaced independently of each other by a respective cis- or

in which a CH unit may also be replaced by a nitrogen atom, an acetylenic CsC group, a divalent phenyl radical, a divalent pyridine radical, a divalent thiophene radical. a divalent Naphthaiinrcst in which one or two CH groups may be replaced by nitrogen atoms, a divalent anthracene radical in which one or two CH groups may be replaced by nitrogen atoms:

More preferably, the optional substituents R I O are independently selected at each occurrence from F and a linear alkyl radical having at least one and at most 37 C atoms.

The compound α-1-adamantylterthiophene is encompassed by formula (I), but may be excluded from the scope of the invention.

As is clear from the above definitions, preferred compounds according to the invention are those of the formulas (IIa) or (IIb):

in which R4 and R5 are independently defined on each occurrence as defined for formula (I), n is as defined for formula (I), and R7, R8 and R9 are each independently hydrogen at each occurrence or as R10 is for formula (I) are defined. Preferably, R7, R8 and R9 are hydrogen.

More preferred within the scope of the invention are compounds of the fins (Ula) or (IIIb):

in which n is as defined for formula (1), and R7, R8 and R9 are independently at each occurrence hydrogen or as RIO are defined for formula (I). Preferred are R7. R8 and R9 are hydrogen.

With particular preference the compounds according to the invention are compounds of the formulas (IVa) or (IVb):

in which n is as defined for formula (I).

The structures of the particularly preferred compounds 2a-4a or 2b-8b according to the invention are illustrated below:

3a

8b

The UV / Vis absorption spectra of the compounds according to the invention are bathochromically shifted with increasing number n of thiophene units. While 2 a with n = 2 at 313.4 nm absorbs in the UVB range, 3a with n = 3 at 360.4 nm already reaches the UVA range and 4a with n = 4 and 396.8 nm the visible spectral range: see Figure 1. The high molar Extraction coefficients. For example, up to 35,600 channels-cn ¹ for 4a are of particular interest for optical applications.

The fluorescence spectra of the compounds according to the invention are distinguished by large Stokes shifts, with maxima at 378.2 nm for 2a, at 3a already in the visible range at 420.5 and 442.7 nm and at 461.7 and 490.0 nm at 4a. Advantageously, the large Stokes shifts are also retained in a solid matrix. Substantial fluorescence quantum efficiencies of up to 43% were determined. Even more surprising and unexpected is the unusually rapid fluorescence decay time of the compounds. For example, a fluorescence lifetime of only 0.36 ns was determined for compound 4a; see Figure 3. The extension of the thiophene chain, which is accompanied by a successive bathochromic shift, has little effect on the fluorescence decay time. Accordingly, the compounds according to the invention can be selected adapted for various applications. The large Slokes shift of the substances is favorable eg for Lichtsammeisysteme, because by the small spectral overlap between absorption and fluorescence spectrum fluorescent light, which is conducted over a longer distance, undergoes little reabsorption by the compound of the invention. If the compounds according to the invention are used instead of in a homogeneous solution in a solid matrix then, surprisingly, the large Stokes shifts (see FIG. 2) and the short fluorescence decay times are essentially retained; This is of particular importance for the technology because the use of liquids, even in capillaries, is relatively complicated and cumbersome. In addition, a large Stokes shift basically opens up the possibility of depopulating the optically excited state. It would be possible in the absorption range of the compounds to excite them optically by a light pulse and to detect the fluorescence immediately thereafter. With a second light pulse at longer wavelengths in the range of fluorescence can produce stimulated fluorescence and thus depopulate the excited state (according to the operation of dye lasers). The sequence of the two pulses can be short, since substantial parts of the fluorescence are already obtained within the first half-life. The transmission of the information content can be increased by suitable modulation methods in a manner known per se.

In addition, the compounds according to the invention have excellent lightfastness and are stable against sunlight for several months.

in particular the simply terminally substituted oligothiophenes (ie compounds of the formula (I) where R 6 = H or the preferred compounds of the formulas (IIa), (IIIa) and (IVa) and also 2a-4a) are in lipophilic solvents, monomers or else Polymer matrices surprisingly well soluble and can therefore be used for optical applications that require homogeneously dispersed, in particular molecularly dispersed substances. While it was expected that oligothiophenes with two terminal substituents (ie compounds of formula (I) with R6 = - C (R1 R2R3) or the preferred compounds of formulas (IIb), (Ulb) and (IVb), and 2b - 8b) are even more soluble, this was surprisingly not the case in practice. Rather, their solubility is significantly lower than that of the monosubstituted terminal oligothiophenes. The solubilizing effect of one terminal group is apparently overcompensated by the second group. The asymmetric substitution with only one terminal group obviously has a special position, which was not to be expected. This may be related to the unsymmetrical substitution, which leads to a kind of liophilic amphiphilic character, with a heteroaromatic and a predominantly aliphatic structural group. For UV / Vis applications in homogeneous solution or in a polymer matrix, therefore, in particular the compounds which are simply terminally substituted are surprisingly well suited.

In this respect, a further aspect of the invention relates to the use of the compounds of the formula (I) according to the invention, in particular of the compounds of the formula (I) with R6 = H or the preferred compounds of the formulas (IIa), (IIIa) and (IVa). and 2a-4a, in optical information collection systems, optical information processing systems, or optical information relaying systems. As preferred examples, there may be mentioned optical polymer waveguides (especially polymeric optical fibers) and optical slip ring systems (also referred to as optical rotary transducers). In such applications, the compounds of the invention can be used in particular as a fluorescent dye and / or frequency converter due to their absorption and fluorescence properties.

Also, the invention provides optical information collection systems. optical information processing systems or optical information transmission systems, preferably optical polymer waveguides (in particular polymeric optical fibers) and optical slip ring systems which contain the compounds of the formula (1) according to the invention, in particular the compounds of the formula (I) where R 6 = H or the preferred Compounds of formulas (IIa), (IIIa) and (IVa), and 2a-4a.

The present invention also provides a polymer composition comprising a solid organic polymer matrix in which one or more compounds of the formula (I) according to the invention are dispersed or together with the Polymer of the polymer matrix form a copolymer. This is preferably a Compound of the formula (I) where R 6 = H, more preferably a compound of the formula (IIa), even more preferably a compound of the formula (IIIa) and particularly preferably a compound of the formula (IVa) or of the formula 2a, 3a, or 4a.

Preference is given to polymer compositions in which one or more compounds of the formula (I) according to the invention are dispersed in a solid organic polymer matrix. In particular, the dispersed form also comprises a molecular disperse form in which a solid solution of the compound of formula (1) is formed in the polymer matrix. A copolymer is particularly present when compounds of the invention, e.g. with the aid of a suitable radical selected from R1-R5, covalently bonded to the polymer of the polymer matrix.

The solid organic polymer matrix may comprise one or more types of polymers. However, polymer blends should preferably be used only insofar as the polymeric constituents are completely homogeneously miscible, so that the polymer matrix as such is a single-phase matrix.

In particular, with regard to said optical applications, the solid organic polymer matrix is preferably transparent, the transparency of the matrix should in particular be given in a wavelength range comprising the absorption band and the fluorescence band of the compound of the invention used or the compounds which by means of a UV / Vis Spectrometer can be determined. The polymer matrix should preferably be transparent to electromagnetic radiation in the UV-IR range, in particular over the entire wavelength range from 350 to 700 nm. In addition, a high refractive index is advantageous for the solid polymer matrix.

Numerous polymeric materials suitable for providing a solid organic polymer matrix, particularly a transparent polymeric matrix, are known in the art. As examples of polymers comprised by the polymer matrix, or of which the polymer matrix may consist, may be mentioned: polyacrylates (including poly (alkyl) acrylates, especially polymethyl methacrylate), halogenated, especially fluorinated polyacrylates, polycyanurates, perfluorocyclobutane polymers (PFCB), Silicones, polycarbonates, polystyrene, cellophane (celloloid), acetylcellulose, polvfluorinated polvethers or polvfluorinated alkanes. Preferred examples are polymethylmethacrylate. the im transparent spectral region, and polycarbonate, which is also characterized by high transparency and high refractive index. Advantageously, the compounds of the invention are also stable under conditions of free-radical polymerization, so that radically polymerized polymers can be suitably used to provide the solid organic polymer matrix.

In the polymer composition is the compound of formula (I), in particular the compound of formula (I) with R6 = I I. or the compound of formula (IIa), the formula (IIIa) of the formula (IVa) or the formula 2 a, 3a or 4a preferably before as a dopant. Exemplary concentrations of the compound according to the invention (or the sum of all the compounds according to the invention, if more than one compound is used) are in the range of 0.01 to 1000 ppm, preferably 0.1 to 500 ppm and particularly preferably 1 to 100 ppm, wherein the indication refers to the parts by weight of the compound of the invention based on the weight of the solid organic polymer matrix.

The compound according to the invention can be introduced into the polymer matrix in various ways, for example by mixing with polymer materials, for example as granules, and melting using extrusion or injection molding methods. However, the compounds according to the invention, in particular the compounds of the formula (I) where R 6 = H, are also surprisingly soluble in liquid monomers. They can therefore also be dissolved in the monomers which are then polymerized, for example methyl methacrylate to polymethyl methacrylate. Processes in which the compound according to the invention is present during the polymerization of the polymer matrix are also suitable, for example, for providing a polymer matrix in which a compound according to the invention forms a copolymer together with the polymer of the polymer matrix. Here, a radical selected from R1 to R5 should be present in the compounds of the invention which can react with the monomers to form the polymer matrix to form a covalent bond. Surprisingly, the free-radical polymerization poses no problems whatsoever, not even with respect to the presence of sulfur in the oligothiophenes of the present invention, and although elevated temperatures (for example, up to 70 ° C) have been used. Finally, the dyes can also be diffused from solvents into the polymer materials. The doping method may suitably be selected depending on the respective technological boundary conditions. The polymer composition of the invention can be made into any suitable form such as a fiber, a plate, a disc, a ring, etc.

A further subject of the invention thus forms optical information collection systems, optical information processing systems or optical information transmission systems, preferably optical polymer waveguides or optical waveguides (in particular polymeric optical fibers) and optical slip ring systems which contain a polymer composition according to the invention. For example, in an optical slip ring system according to the invention, typically a light guide is used. e.g. a round optical fiber, from the above-described polymer composition with a compound of formula (I) according to the invention (in particular a compound of formula (I) with R6 = II, or a compound of formula (IIa), the formula (IIIa) of the formula (IVa) or the formula 2a, 3a or 4a), light, in particular modulated light, from a transmitter, converts it into fluorescent light and conducts it to a receiver, without the light guide is in mechanical contact with the transmitter. The optical slip ring can be designed for rotatable systems in a round shape.

The transfer of information with the aid of a polymer composition according to the invention can be carried out, for example, according to the principle of the fluorescence solar collector (IL Langhals, Nachr. Chem. Tech. Lab. 1980, 25, 716-718, Chem. Abstr. 1981, 95, R9816q), in which The polymer composition can form, for example, a plane-parallel plate or else a round light guide, which can also be arranged in the form of a round optical slip ring in order to ensure signal transmission from all directions of rotation. Light can penetrate from all spatial directions with refraction in the polymer composition and is absorbed by the present invention there compound. 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 strikes the surface flat, is reflected by total reflection back into the polymer composition and guided there to the edge surface. For example, in the case of optical slip rings, with regard to the light guide, it is possible to radiate mechanically robustly from all directions of rotation and to detect it at the end of the light guide. As explained above, the di-terminally substituted compounds of the formula (I) with R 6 = -C (R 1 R 2 R 3), or the preferred compounds of the formulas (IIb), (IIIB), (IVb) and 2b-8b, are simple compared with the corresponding ones terminally substituted compounds have a significantly reduced solubility in lipophilic media. This property, as well as their color and light stability, makes the applications of such compounds interesting as color pigments. This preferably applies to compounds of the formula (I) where R 6 = -C (R 1 R 2 R 3), or to compounds of the formulas (IIb), (IIIB), (IVb) with values of n> 4, particularly preferably as values for n here are 4, 6 and 8. For example, for n = 6 an orange-red solid is obtained and for n = 8 a brilliant bright red solid.

Here also has an advantageous effect that the inventive double-terminally substituted compounds of formula (I) with R6 - -C (R1R2R3), or the preferred compounds of the formulas (IIb), (IHb), (IVb) and 2b-8b from simply terminally substituted compounds can be prepared by an efficient coupling reaction described here. Because of their good solubility discussed above, the starting compounds can be conveniently prepared in high purity and uniformity, conventional purification methods such as recrystallization or chromatography can be used. Even unreacted, simply terminally substituted compounds can be readily removed from the reaction mixture in the preparation of the two-terminally substituted compounds in this manner, so that the di-terminally substituted compounds of the formula (1) according to the invention with R 6 = -C (R 1 R 2 R 3) , or the preferred compounds of the formulas (IIb), (IIIB), (IVb) and 2b-8b in a high purity, and thus can be produced in brilliant shades. Color mixtures generally lead to dull, less brilliant

It should be noted, however, that the compounds of formula (I) and the preferred embodiments of the present invention such as (IIa), (IIb), (IIIa), (IIIb), (IVa) and (IVb) are not limited to the above-mentioned applications are limited. Due to their absorption and fluorescence properties or their properties as colorants, they are also suitable for other applications. Before the background of the foregoing description, one skilled in the art will readily be able to select the most suitable compound or compounds for the particular application. By way of example may be mentioned the use as pigments or colorants for dyeing purposes, also for decorative and artistic purposes, such as for example for glue colors and related colors such as watercolor paints and watercolors and inks for inkjet printers, paper inks, printing inks, 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, novolacs. Nitrocellulose lacquers (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, polyvinylbenzylchloride, polymethylmethacrylate, polyethylene. Polypropylene, polyvinyl acetate, polyacrylonitrile, polyacrolein, polybutadiene, polybutadiene or polyisoprene or the copolymers of said monomers, for coloring natural substances, examples being paper, wood, straw or natural fiber materials such as wool, hair, pet hair, bristles, Cotton, jute, sisal, hemp, flax or their transformation products such as the viscose fiber, nitrate silk or copper rayon (rayon). as mordant dyes, for example for coloring natural substances, examples are paper, wood, straw, or natural fiber materials such as wool, hair, pet hair, bristles, cotton, jute. Sisal. Hemp, flax or 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 colorants, eg for coloring paints, lacquers and other paints, paper inks, printing inks, inks and other colors for writing and writing purposes, in addition to other colors, in which a certain shade of shade is to be achieved, particularly bright shades are preferred.

Further examples are the use of the compounds according to the invention for labeling. Security and display purposes, in particular with regard to their fluorescence, such as dyes or fluorescent dyes for signal colors, preferably for the visual highlighting of lettering and drawings or other graphic products, for marking signs and other objects and in display elements for many display, Note and marking purposes in which a particular visual color impression is to be achieved, for passive display elements, traffic signs and traffic signs, such as traffic lights for security marking purposes, wherein the high chemical and photochemical stability and possibly also the fluorescence of the substances of importance is preferred this for checks, check cards, banknotes. Coupons, documents, identity documents and the like, in which a particular, unmistakable color impression is to be achieved, for marking objects for machine recognition of these objects via fluorescence, the automatic recognition of articles for sorting, eg also for the recycling of plastics, is preferred as fluorescent dyes for machine-readable markings, preferred are alphanumeric prints or barcodes, as dyes in ink jet printers in homogeneous solution, preferably as fluorescent ink, as dyes or fluorescent dyes in display, illumination or image converter systems, where the excitation by electrons, ions or UV radiation takes place, for example in fluorescence displays , Braunsehen tubes or in fluorescent tubes, for tracer purposes. For example, in biochemistry, medicine, technology and natural sciences, here, the dyes may be covalently linked to substrates or on minor valences such as hydrogen bonds or hydrophobic interactions (adsorption), as dyes or fluorescent dyes in chemiluminescent zenzsy, eg in chemiluminescent light rods, in luminescence immunoassays or other luminescence detection method and as a material for leak testing of closed systems.

Further examples which may be mentioned are the use of the compounds according to the invention as functional materials, for example in data memories, preferably in optical memories, such as the CD or DVD disks, in OLEDS (organic light-emitting diodes), in photovoltaic systems, as pigments in the US Pat Electrophotography: eg for dry copying systems (Xerox process) and laser printers ("Non-Impact Printing"). for the frequency conversion of light, for example to make shortwave light from longer wavelength, visible light, as a starting material for superconducting organic materials, as fluorescent dyes in scintillators, as dyes or fluorescent dyes in other optical Lichtsammeisystemen, such 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, for example 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 Process, as dyes or fluorescent dyes as part of a semiconductor integrated circuit, the dyes as such or in conjunction with other semiconductors, for example i n form of 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, eg for frequency doubling and frequency tripling of laser light.

For the preparation of the compounds according to the invention, advantageously first a thiophene or an oligothiophene is terminally substituted. For attachment of a terminal substituent -C (R1R2R3), the thiophene may be halogenated in a neighboring position of the sulfur to obtain a halothiophene or a halo-oligothiophene, respectively. As Ilalogen comes here in particular Cl, Br and I, preferably Br used. The halothiophene or a halo-oligothiophene is then reacted with a zinc halide of the formula (R 1 R 2 R 3) C-ZnX, in particular with a zinc chloride (R 1 R 2 R 3) C-ZnCl, catalysed by a palladium compound, in particular with palladium acetate and SPhos complexes (SPhos = 2). Dic} 'clohexylphosphino-2', ^6'-dimetox}? biphenyl) is reacted (according to the model of the Negishi Kreuzkuppkmg). In the formulas, R 1, R 2 and R 3 are as defined above for the compounds of the invention, X is a halogen selected from Cl, Br and I, in particular Cl. In this way, surprisingly smooth a simply terminally substituted thiophene, such as the thiophenoadamantane 1 a. and the simply terminally substituted oligothiophenes of the formula (I) where R 6 = H, for example the compounds 2a and 3a, are obtained.

In order to set the number of linked thiophene units in the oligothiophene chain of the compounds of the formula (I) where R 6 = 1, a process is also available in which a simple terminally substituted thiophene or a singly terminally substituted oligothiophene of the formula (V)

wherein R1 to RS are as defined above for formula (I) (including all preferred embodiments), and p is an integer of 1 to 6, preferably 2 or 3. halogenated with CL Br or 1. Here in particular the bromination, eg with NBS (N-bromosuccinimide), has proven itself. Thus, halogen-containing (oligo) thiophenes of the formula (VI) which are monosubstituted or substituted by a radical -C (R1R2R3) are obtained as a synthetic intermediate:

wherein R 1 to R 5 are as defined above (including all preferred embodiments), X is Cl, Br or I and preferably is Br, and q is an integer from 1 to 12, preferably from 1 to 6, more preferably from 1 to 3 , and in particular 2 or 3. The resulting halogen derivative (VI) can be subjected to a palladium-catalyzed coupling reaction with a metalated thiophene, eg, 2-thienylzinc chloride, to obtain a compound of the formula (I) in which the number of thiophene units increases by 1 in the formula (VI) was increased (ie n = q + 1).

As is already clear from the definition of the radicals R 1 to R 5, preference is given to compounds of the formulas (V) and (VI) as starting compounds and intermediates which correspond to the formulas (Va) or (V)

wherein the radicals R4 to R9 and X and p and q are as defined above.

More preferred are compounds of formulas (V) and (VI) as starting compounds and intermediates. which correspond to the formulas (Vb) or (VIb):

wherein the radicals R7 to R9 and X and p and q are as defined above.

Most preferred compounds of the formulas (V) and (VI) are starting compounds and intermediates which correspond to the formulas (Vc) or (Never):

wherein X, p and q are as defined above.

For the preparation of the double terminally substituted compounds of the formula (I) according to the invention with R 6 = -C (R 1 R 2 R 3), different synthesis strategies are available.

According to the above procedure, oligothiophenes can be halogenated twice in each case in a Naehbarposition the Schw efels terminal. As halogens, in particular CL Br and I, preferably Br, are also used here. Subsequently, the doubly terminal halogenated oligothiophene with a sufficient amount of zinc halide of the formula (R1 R2R3) C-ZnX, in particular with a zinc chloride (R1 R2R3) C-ZnCl. catalyzed by a palladium compound, in particular with palladium acetate and SPhos complexes to achieve a two-fold terminal substitution.

However, the preparation of the doubly substituted oligothiophenes of the formula (I) with R 6 = -C (R 1 R 2 R 3) starting from monofunctionally substituted oligohiophenes of the formula (VII) has proved to be particularly advantageous

wherein R 1 to R 5 are as defined above (including all preferred embodiments), and r is an integer of 1 to 6, preferably 2 to 4. It can be realized surprisingly efficiently in the presence of an iron (III) compound, in particular anhydrous iron (III) chloride. The reaction is preferably carried out in a lipophilic and non-oxidizing solvent, which is typically anhydrous. Preferred examples are chloroform and dichloromethane, especially chloroform. The iron (III) chloride does not have to be completely anhydrous, a sufficiently high proportion of anhydrous iron (III) chloride is sufficient. In addition, the implementation takes place under remarkably mild and surprisingly mild conditions. The reaction temperature is typically in the range of 0 to 100 ° C, the reaction can be carried out advantageously already at room temperature, for example from 20 to below the boiling point of the solvent, for example 60 ° C, and with surprisingly high yields, the yields for others significantly exceed known reactions in the oligothiophenes. Finally, it has to be particularly mentioned that for the synthesis no activation of the Ohgothiophene, such as by a bromination or metallation, is required; this makes the process economical and cost-effective, in particular because anhydrous iron (III) chloride is a toxicologically and ecologically unobjectionable bulk chemical. In this synthesis, the Ohgothiophene arise directly as pure substances, traces of starting compounds can be easily removed from the reaction products, with solvents such as toluene or chloroform. In this procedure, the use of a single starting substance of the formula (VII) is preferred in order to obtain a chemically well-defined product. In principle, however, it is also possible to use mixtures of starting compounds of the formula (VII), which leads to mixtures of di-terminally substituted oligothiophenes having different numbers of thiophene units.

As is already clear from the definition of the radicals R 1 to R 5, preference is given to compounds of the formula (VII) as starting compounds which correspond to the formula (Vfla):

wherein the radicals R4 to R9 and X and r are as defined above.

More preferred are compounds of the formula (V) as starting compounds which correspond to the formula (VIIb):

wherein the radicals R7 to R9 and X and r are as defined above.

Most preferred are compounds of formulas (V) as starting compounds and intermediates. corresponding to the formula (VIIc):

wherein X, and r are as defined above.

Essential aspects of the invention are summarized in the following points.

1. Compound of formula (I):

in which

R 1, R 2 and R 3 are each independently selected from an alkyl group, an alkenyl group and an aryl group which may be substituted with one or more substituents RIO.

wherein two radicals selected from R 1, R 2 and R 3, each independently representing an alkyl radical or an alkenyl radical, together with the carbon to which they are attached may be linked to a cycloalkane radical or a cycloalkyl radical which may be substituted by one or more substituents RIO

or all three of R 1, R 2 and R 3, each independently representing an alkyl radical or an alkenyl radical, together with the carbon to which they are attached may be linked to a bridged cycloalkyl radical or bridged cycloalkane radical which may be substituted with one or more multiple substituents RIO;

R4 and R5 independently of each occurrence are selected from hydrogen, F, Cl, Br, I and a linear alkyl radical having at least one and at most 37 C atoms,

wherein in the alkyl radical, one to 10 CH 2 units may independently be replaced by each of a carbonyl group, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, a cis- or "m" -CH = CH- group in which a CH unit may also be replaced by a nitrogen atom, an acetylenic C = C group, a divalent phenyl radical, a divalent pyridine radical, a divalent thiophene radical, a divalent naphthalene radical in which one or two CH groups may be replaced by nitrogen atoms divalent anthracene radical in which one or two Cl I groups may be replaced by nitrogen atoms;

and wherein in the alkyl radical up to 12 individual hydrogen atoms of the CH ₂ groups can each be independently replaced by the same carbon atoms by a halogen, a cyano group or a linear alkyl chain having up to 18 carbon atoms. in which one to 6 CHi units can be replaced independently of one another by a carbonyl group, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, an eis or fr <ms-CH = CH group in which a CH unit may also be replaced by a nitrogen atom, an acetylenic C = C group, a divalent phenyl radical, a divalent pyridine radical, a divalent thiophene radical, a divalent naphthalene radical in which one or two CII groups may be replaced by nitrogen atoms, a divalent Antliracenrest in which one or two CH groups may be replaced by nitrogen atoms, and wherein up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl chain each independently may also be replaced by the same carbon atoms by a halogen, a cyano group or a linear alkyl chain having up to 18 carbon atoms, in which one to 6 CH ₂ units may be replaced independently by a carbonyl group, an oxygen atom, a Sulfur atom, a selenium atom, a tellurium atom, an ice or

in which a CH unit may also be replaced by a nitrogen atom, an acetylenic C ^ C group, a divalent phenyl radical, a divalent pyridine radical, a divalent thiophene radical, a divalent naphthalene radical in which one or two CH groups may be replaced by nitrogen atoms a divalent antiracea residue wherein one or two CII groups may be replaced by nitrogen atoms;

and wherein the free valencies of methine groups or of quaternary C atoms in such alkyl radicals can also be linked in pairs, so that a ring is formed:

R6 is selected from H and a radical -C (R1 R2R3) wherein R1, R2 and R3 are as defined above: n represents an integer from 2 to 12; and the optional substituents R 1 O to R 1, R 2 and / or R 3 are independently selected from F, Cl, Br, I and a linear alkyl radical as defined above for R 4 and R 5.

Compound according to item 1, wherein R6 is hydrogen.

Compound according to item 1, which is a compound of formula (IIa)

in which R4 and R5 are independently of each other on each occurrence as defined for formula (I), n is as defined for formula (I), and R7, R8 and R9 independently of one another at each occurrence are hydrogen or as R10 is for formula (I) are defined. Compound according to item 1, which is a compound of the formula (IIIa)

(IIIa) in which n is as defined for formula (I), and R7. R8 and R9 independently of each other are hydrogen or as RI 0 are defined for formula (I). Compound according to item 1, which is a compound of formula (IVa)

where n is as defined for formula (1). A compound according to any one of items 2 to 5, wherein n is an integer from 2 to 6, preferably to 4. Compound according to item 1, which is one of the following compounds 2a:

4a

A compound according to item 1, wherein R 6 is -C (R 1 R 2 R 3) and R 1, R 2 and R 3 are independently defined as for formula (1).

Compound according to item 1, which is a compound of the formula (IIb)

wherein R4 and R5 are independently in each occurrence as defined for formula (I), n is as defined for formula (I), and R7, R8 and R9 are each independently hydrogen at each occurrence or as RI 0 for formula (I ) are defined. Compound according to item 1, which is a compound of formula (IIIb)

in which n is as defined for formula (I). and R7, R8 and R9 are independently hydrogen at each occurrence, or as R110 is defined for formula (1). Compound according to item 1, which is a compound of formula (IVb)

where n is as defined for formula (I). A compound according to any one of items 8 to 11, wherein n is an integer from 4 to 12, preferably from 4 to 8. Compound according to item 1, which is one of the following compounds:

2b 4b

8b, a polymer composition comprising a solid organic polymer matrix, in which a compound according to any one of items 1 to 13, preferably the points 2 to 7, dispersed or forms together with the polymer of the polymer matrix a copolymer. , The polymer composition of item 14, wherein the solid organic polymer matrix comprises a polymer selected from polyacrylates, poly (alkyl) acrylates, halogenated, polyacrylates, halogenated poly (alkyl) acrylates, polycyanurate, perfluorocyclobutane polymers, silicones, polycarbonates, polystyrene, ceilophane , Acetylcellulose, polyfluorinated polyethers and polyfluorinated alkanes. , The polymer composition of item 15, wherein the solid organic polymer matrix comprises a polymethylmethacrylate or polycarbonate. , A polymer composition according to any one of items 14 to 16, wherein the concentration of the compound according to any one of items 1 to 13, preferably items 2 to 7, in the polymer matrix is in the range of 0.01 to 1000 ppm. , An optical polymer waveguide or slip ring optical system comprising a polymer composition according to any one of items 14 to 17.. Use of a compound according to any of items 1 to 13, preferably of items 2 to 7, as a fluorescent dye in optical information collection systems, optical information processing systems or optical information systems, in particular in polymer optical waveguides or optical waveguide or optical flooding systems. Use of the polymer composition according to any one of items 14 to 17 as a photoconductive material. Use of the polymer composition according to any one of items 14 to 17 as a photoconductive material in an optical slip ring system. Use of a compound according to any one of items 1 to 13, preferably points 2 to 7, as a frequency converter in optical information collecting, information processing and forwarding systems, in particular in optical light guides, preferably in fast optical systems. Use of a compound according to one of the items 1 to 13, preferably points 2 to 7 in optical slip ring systems, by an optical waveguide, eg a round optical waveguide, preferably of organic polymer material, in particular of polymethyl methacrylate (PMMA, Plexiglas), which with a compound according to a is doped points 2 to 7, without any mechanical contact light, in particular modulated light from a transmitter, convert it into fluorescent light and can lead to a receiver. The optical slip ring can be designed for rotatable systems in a round shape. Use of a compound according to any one of items 8 to 13 as a colored pigment. A process for the preparation of a compound according to any one of items 1 to 1 3, which comprises reacting a halogenophthalene or a halogeno-oligothiophene with a zinc halide of the formula (R 1 R 2 R 3) C-ZnX. wherein R 1, R 2 and R 3 are independently defined as for the formulas in items 1 to 13 and X is Cl, Br or I, catalyzed by a palladium compound.

Process for the preparation of a compound according to one of the items 8 to 13, where two identical or different compounds of the formula (VII)

wherein R 1 to R 5 are independently defined as for the formulas in items 8 to 13, and r is an integer of 1 to 6, coupled in the presence of anhydrous iron (III) chloride to a compound according to any one of items 8 to 13 become.

Compound of the formula (VI)

wherein R 1 to R 5 are independently defined as in item 1, X is Cl, Br or I, and q is an integer of 1 to 6.

Examples

General. IR Spectra: Perkin Elmer 1420 Ratio Recording Infrared Spectrometer, FT 1000; UV / Vis spectra: Varian Cary 5000; Fluorescence spectra: Varian Eclipse; Fluorescence lifetimes: NKT-Laser Super Extreme EXB-4 from NKT Photonics A / S, Edinburgh Instruments Ltd. Monochromator, PicoHarp 300 from PicoQuant GmbH and PMA-C 192-NM photomultiplier for detection; NMR spectroscopy: Varian Vnmrs 600 (600 MHz): mass spectrometry: Finnigan MAT 95. Fluorescence quantum yields were analogous to H. Langhals. J. Karolin, L, B.-A. Johansson, J. Chem. Soc, Faraday Trans. 1998, 94, 2919-2922. Production Example 1: Adamantan-1-yl zinc chloride

In a dried glass apparatus, lithium chloride (233 mg, 5.5 mmol) was heated in a fine vacuum with a hot air blower for 5 min to about 400 ° C, allowed to cool to room temperature, aerated with nitrogen, with magnesium turnings (241 mg, 10.0 mmol, activated with 47.0 mg , 0.25 mmol, 1, 2-dibromoethane and 27.2 mg, 0.25 mmol, TMSCl), ZnCl ₂ (5.5 mL, 1 M in THF) and 1 -bromoadamantane (1.08 g, 5.0 mmol) with stirring over a period of 2 h 25 ° C added: An iodometric titration (A. Krasovski, P. Knöchel, Synlhesis 2006, 890-891) showed a content of 0.34 M (85%).

H erstel 1 un b e s p e c ie 1 2: 2- (adainantan-l-vT) thiophene (la)

A freshly prepared solution of adamantane-1-ylzinc chloride (3.2 mL, 1.1 mmol, 0.34 M in THF) was mixed with Pd (OAc) ₂ (2 mg, 0.01 mmol). SPhos (8 mg, 0.02 mmol) and 2-bromothiophene (147 mg, 0.9 mmol) stirred for 2 h at 50 ° C, by adding sat. aqueous NH ₄ Cl (10 mL), extracted with ethyl acetate, dried with sodium sulfate, evaporated in vacuo and purified by flash chromatography (silica gel, pentane / diethyl ether 100: 1). Y. 120 mg (61%) of a colorless solid, mp 66.1-67.2 ° C. IR (ATR): v = 3098, 3070, 2898, 2846, 1526, 1446, 1342, 1314, 1261, 1228, 1100, 1077, 1052, 1004, 966, 850, 823, 808, 703, 694. 686 cm ^"1. Ή NMR (300 MHz, CDC1 ₃ ): δ = 7.14 (dd, J = 5.0 Hz, 1 .1 Hz, 1 H), 7.01-6.89 (m, 1H), 6.83 (dd = 3.5Hz, 1 .2Hz. 1H), 2.10 (bs, 3H), 2.00 (d, J = 2.8Hz, 6H), 1.88-1 .71ppm (m, 6 IL). ^{, 3} C NMR (75 MHz, CDCl ₃ ): S = 158.3, 126.3, 121.9, 120.1, 45.0, 36.7, 36.2, 28.9 ppm MS (70 eV, Ei), m / z (%) = 218 {K'f, 71), 175 (7), 163 (5), 162 (13), 161 (100), 128 (6), 124 (15), 97 (6), HRMS (EI), m / z calc _{I 4} H ₁₈ S 218.1 129. Gef. 218.1 144: A = +} .5 mmu.

Example 1: 5- (adamantane-l) -2,2'-dithioph

A freshly prepared solution of adamantan-1-ylzinc chloride (3.2 mL, 1.1 mmol, 0.34 in THF) was mixed with Pd (OAc) ₂ (2 mg, 0.01 mmol), SPhos (8 mg, 0.02 mmol) and 5-bromo-2 , 2'-dithiophene (221 mg, 0.9 mmol) stirred for 2 h at 50 ° C, by adding sat. aqueous NH ₄ Cl (10 mL), extracted with ethyl acetate, dried with sodium sulfate, evaporated in vacuo and purified by flash chromatography (silica gel, pentane). Y. 157 mg (58%) of colorless solid, mp 69.9-70.7 ° C, IR (ATR): v = 3119, 3069, 2910, 2898, 2846, 1512, 1460, 1445, 1428, 1342, 1318, 1204, 1 184, 1100, 1060, 1003, 976, 887, 876, 840, 823, 810, 797, 688, 684 cm ^-1 . ¹ H NMR (600 MHz, CDCl ₃ ): δ = 7.17 (dd, J = 5.1 Hz, 1.2 Hz, 1 H), 7.1 1 (dd, J = 3.6 Hz, 1.1 Hz, 1 H), 7.05-6.96 (m, 2 II) 6.72 (d, J = 3.6 Hz, 1 H), 2.10 (bs, 3H), 2.06-1.93 (m, 6H), 1.87-1.71 ppm (m, 6H), ^B C NMR (150 MHz, CDCl ₃ ): <5 = 157.6, 138.1, 133.9, 127.6, 123.7, 123.1, 122.9, 121.0, 44.8, 36.6, 36.4, 28.9 ppm UV / Vis (CHC1 ₃ ): / x (c) = 313.4 nm (16000) Fluorescence (CHCl ₃ ): n max ⁼ 478.2. Quantum fluorescence quantitate (CHQ ^ / IE _X = 313.4 nm, 313.4 l / cm = 0.159, standard: perylene-3,4,9,10-tetracarboxylic acid tetramethyl ester with Φ-1.00): 0.04 MS (70 eV, EI) , m / z (%) = 300 (Vi.100), 257 (4), 245 (6), 244 (13), 243 (63), 210 (11), 209 (4), 206 (12), 121 (5), 61 (4) 45 (4), 43 (26) HRMS (EI) m / z Calcd C, gII ₂ os ₂ 300.1006, Found 300.0996...; - mmu -1.0.

Example 2: 5- (adamantane l - l) -2,2 ': ^5, 2 "-terthiophene (3a)

A freshly prepared solution of adamantane-1-ylzinc chloride (3.2 mL, 1.1 mmol, 0.34 in

THF) was treated with Pd (OAc) ₂ (2 mg, 0.01 mmol), SPhos (8 mg, 0.02 mmol) and 5-bromo-

2,2 ': 5'.2 "-terthiophene (295 mg, 0.9 mmol) stirred at 50 ° C for 2 h, by adding sat

NPI4CI (10 mL), extracted with ethyl acetate, dried with sodium sulfate, evaporated in vacuo and purified by flash chromatography (silica gel, pentane diethyl ether 100: 1).

Y. (220 mg, 64%) yellow solid; M.p. 171 .0-173.0 ° C. 1R (ATR): v = 3072, 3063,

2954, 2902, 2847, 1514, 1495, 1460, 1447, 1423, 1377, 1364, 1342, 1315, 1232, 1207, 1 193,

. 1159, 1099, 1058, 1004, 965, 912, 831, 790, 675 cm ^'' Ί ΐ- MR (600 MHz, CDCI _3): ö = 7.25-

7.13 (m, 2H), 7.10-6.96 (m, 4H), 6.76-6.67 (m, 1H), 2.10 (bs, 3H), 1.99 (d, J = 2.7Hz, 6H) .

1.84-1.70 ppm (m, 6H). ^{, 3} C-NMR (150 MHz, CDCl ₃ ): δ = 157.9, 137.4, 137.0. 135.5, 133.6,

127.8. 124.3, 124.2, 123.4, 123.4, 123.1, 121.1, 44.8, 36.6, 36.5, 28.8 ppm. UV / Vis (CHCi): _ΙΗΚ (£) = 360.4 nm (21400). Fluorescence (CHC1 ₃ ): ™ χ ( _re i) = 420.5 (0.88), 442.7 in (1.00). Fluoreszenquantenausb. (CHC1 _3, Ä _Ex = 360.4 nm, 300.4 nm £ / cm j = 0.102, standard: perylene 3,4,9, 10-tetracarbonsäuretetramethylester with Φ = 1.00): 0.12. MS (70eV, EI), m / z (%) = 382 (A, 100). 327 (5), 326 (6), 325 (27), 292 (5), 288 (6), 261 (5), 248 (22), 42 (5), 41 (6). HRMS (EI), m / z Ber. C22H22S3 382.0884, Gef. 382.0870; Δ = - \ Α mmu.

Example 3: 5- (Adamanian-1-yl) -2,2 ': 5', 2 ": 5", 2 '"- qiiatert} iioph

LiCl (670 mg, 15.8 mmol) was heated in a fine vacuum to about 300 ° C, allowed to cool, shaved under Argo with magnesium (740 mg, 30.4 mmol, activated with 1, 2-dibromoethane, 1 15 mg, 0.61 mmmol and TMSC1 , 66.6 mg, 0.61 mmol), dry THF (13 mL), with ZnCL solution (13.5 mL, 13.5 mmol, 1.0 M in THF) and then with 2-bromothiophene (2.00 g, 12.3 mmol). Stirred for 4 h at room temperature, allowed to settle and centrifugation separated from the solid and iodometrically analyzed for the content of zinc reagent (0.95 M in THF). 1 .6 mL of the solution (1.5 mmol, 0.95 in THF) was treated with 5- (adamantane-1-yl) -5 "-bromo-2.2 ': 5', 2" -terthiophene (350 mg, 0.76 mmol) and Pd (PPh ₃ ) ₄ (44 mg, 0.04 mmol), stirred for 3 h at 50 ° C, with saturated aqueous NH4Cl solution (10 mL), extracted with ethyl acetate (3 ^χ 20 mL), dried with Na? S0, in Vacuum evaporated and fiashchromatographiert (silica gel, pentane L) ieth> ether = 97: 3). Y. 1 94 mg (55%), yellow solid, mp 167.4-1 70.8 ° C. 1R (ATR): v = 2897, 2844. 1500, 1444, 1435, 1425, 1220, 1069, 1046, 855, 831. 822, 791, 760, 740, 734, 679, 668, 652 cm ^-1 . 1 H-NMR (300 spme, CDCl 3): S = 7.21 (dd, J = 5.08, 1.23 Hz, 1 H), 7.16 (dd, J = 3.57, 1.10 Hz, 1 fl), 7.07-7.06 i m 1 H), 7.04 (ie J - 3.57 Hz, 2 H), 7.02-6.99 (m, 3 H), 6.71 (ie J = 3.57Hz, 1H), 2.1 1 -2.06 (m, 3H), 2.02-1.91 (m, 6I), 1.82-1.71 ppm (m, 6H) ¹³ CN R (75 MHz, CDCl 3): S = 158.0, 137.1, 137.1, 136.1, 136.0, 135.1, 133.5, 127.9, 124.4, 124.3, 124.2, 124.0, 123.6, 123.5, 123.2, 121.1, 44.8, 36.6, 36.5, 28.8 ppm UV / Vis (CHCl ₃ ): / Lax iβ) = 396.8 nm (35600) Fluorescence (CFIC1 ₃ ): l _max (/ _re i) = 461.7 (0.92), 490.0 nm (1.00), fluorescence quantum yield (CHCl 3 .A _ex = 396.8 nm, £ 396.8 nm _/ Ί cm = 0.0385, standard: perylene-3,4,9,10-tetracarboxylic acid tetramethyl ester with Φ = 1.00): 0.43, MS (70 eV, EI), m / z (%) = 464 (A, 100) 407 (1 1), 406 (3), 343 (3), 204 (3), 61 (4), 45 (3), 43 (25), HRMS (EI), m / z Ber, C26H24S4 464.0761, Gef. 464.0752; Δ = -0.9 mmu. Example 4: 2- (adamantan-1-yl) -5-bromothiophene

2- (Adamantan-1-yl) thiophene (310 mg, 1.41 mmol) was dissolved in dry chloroform (10 mL) under argon, added with -V-bromosuccinimide (265 mg, 1.49 mmol), stirred at room temperature for 12 h of distilled. Water (10 mL), shaken with ethyl acetate (3 x 15 mL), dried over sodium sulfate and evaporated in vacuo. Y. 410 mg (98%) of colorless solid, mp. 82.7-84.9 ° C. 1R (ATR): v = 2904, 2843, 1726, 1533, 1442, 1344, 1316, 1256, 1212, 1101, 1059, 1004, 970, 961. 953, 950, 813, 788, 767. 679 cm. iT-XMR (300 MHz, CDC1 ₃ ): δ = 6.86 (d, J = 3.9Hz, 1 II). 6.56 (d, J = 3.9Hz, 1H), 2.10-2.05 (m, 3H), 1.99-1.84 (m, 6H), 1.79-1.69 ppm (m, 6H). ¹³ C-NMR (75 MHz, CDCl ₃ ): δ = 159.9, 129.1, 120.6, 108.4, 44.7, 36.7, 36.5, 28.8 ppm. MS (70 eV, El), m / z (%) = 298 (Af. 41), 296 t. 46), 241 (38), 240 (1 1). 239 (38), 204 (18), 160 (76), 149 (18), 135 (100), 15 (19), 93 (35), 91 (32). 83 (20), 79 (47). HRMS (EI), m / z Ber. Ci ₄ H ₁₆ BrS 296.0234, Gef. 296.0199; Δ = -3.5 mmu.

Example 5: 5- (adamantane-1-yl) -5'-bromo-2,2'-dithiopfaene

5- (adamantan-1-yl) -2,2'-dithiophene (129 mg, 0.43 mmol) was dissolved in dry chloroform (5 mL) under argon, ^'' -bromsuccinimide (80 mg, 0.45 mmol) added, 12 h stirred at room temperature, with distill. Water (5 mL), shaken out with ethyl acetate (3 ^× 10 mL), dried over sodium sulfate and evaporated in vacuo. Y. 160 mg (98%) of colorless solid, mp. 98.5-100.9 ° C. IR (ATR): v = 2902, 2845, 174 t, 1513, 1444, 1426, 1237, 1220, 1200, 1101, 1061, 1054, 1003, 965, 869, 799, 786, 688 cm ^"1 ^H.! NMR (300 MHz, CDCl ₃ ): δ = 6.94 (d, J = 3.6 Hz, 2 II) 6.83 (d, J = 3.9 Hz, 1 H), 6.70 (d, -3.6 Hz, 1 H), 2.10 - 2.07 (m, 3H), 1 .99-1 .96 (m, 6H), 1 .79-1.76 ppm (m, 6H). ^{, 3} C-NMR (75 MHz, CDCl3): δ = 158.2, 139.6, 132.8, 130.5, 123.5, 123.0, 121.1, 1 10.0, 44.8, 36.5, 36.5, 28.8 ppm, MS (70 eV, EI), m / z (%) = 380 {M 100), 378 (, 92), 324 (1 1), 323 (50), 322 (13), 321 (44), 286 (12), 284 ( 1 1), 242 (25). HRMS (EI), mz Ber. C, _s Hi ₉ BrS ₂ 378.0112, Gef. 378.0107; Δ = + 0.5 mmu.

Example 6: 5- (Adamanian-1-yl) -5 "-bromo-2,2 *: 5 ', 2" -terthiophene

5- (adamantan-1-yl) -2,2 ': 5', 2 "-terthiophene (180mg, 0.4mmol) was dissolved under argon in dry chloroform (10mL), with Λ'-bromosuccinimide (75mg, 0.42 mmol), stirred at room temperature for 16 h, mixed with distilled water (5 ml), extracted with ethyl acetate (3 × 10 ml), dried over sodium sulphate and evaporated in vacuo, yielded (18 mg, 98%) colorless Solid, mp 154.6-157.3 ° C IR (ATR): v = 3079, 3063, 2900, 2846, 1506, 1445, 1426, 1343, 1315, 1248, 1225, 1 194, 1 101, 1064, 1052, 1003 , 969, 892, 853, 788, 692, 684, 654 cm ^"1 . 1 H NMR (300 MHz, CDCl ₃ ): δ = 7.14-6. 1 (m, 5H), 6.72 (d, J = 3.6Hz, 1H), 2.09 (bs, 3H), 2.04-1.89 (m, 6H), 1.98- 1.67ppm (m, 6H). ^{i 3} C-MR (75 MHz, CDCl 3): δ = 192.4, 158.2, 138.8, 137.5, 134.3. 133.3, 130.6, 124.5, 123.4. 123.4, 121.2, 1 10.7, 44.8, 36.6, 36.5, 28.8 ppm. MS (70 eV, ΕΓ). m / z (%) = 461 (M 100), 459 (hf, 90), 406 (7), 405 (25), 404 (8), 403 (23), 368 (5), 366 (6), 203 (6). HRMS (EI), m / z Ber. C ₂₂ H ₂ iBrS ₃ 461.9968. Gef. 461.9951; Δ = -1.7 mmu.

Example 7: 5,5'-Di (adamantan-1-y!) - 2,2'-dithiophene (2b)

A freshly prepared solution of adamantan-1-ylzinc chloride (3.5 mL, 1.0 mmol, 0.29 in LHF) was treated with Pd (OAc) i (2 mg, 0.01 mmol), SPhos (8 mg, 0.02 mmol), and 5.5 ^* Dibromo-2,2'-dithiophene (129.6 mg, 0.40 mmol) stirred for 3 h at 50 ° C, by adding sat. aqueous NH ₄ Cl (10 mL). extracted with ethyl acetate, dried with sodium sulfate, evaporated in vacuo and purified by flash chromatography (silica gel, hexane / diethyl ether 24: 1). Y. 46 mg (26%) of colorless solid, mp> 250 ° C. IR (ATR) v-2896, 2843, 1524, 1445, 1341, 1312, 1254, 1201, 1100, 1065, 1003, 974, 876, 809, 791, 682 cn ". Ή NMR (300 MHz, CDCl 3): 6 = 6.90 (d, J = 3.5 Hz. 2H), 6.66 (d, J = 3.3 Hz. 2H), 2.12-2.04 (m, 6H), 2.00- 1.93 (m, 12H), 1.80-1.71 ppm (m, 12H). ¹³ C NMR (75 MHz, CDCl ₃ ): δ = 156.9, 134.6, 122.3, 120.7, 44.8, 36.6, 36.4, 28.9 ppm. UV / Vis (CHC1 ₃ ): η «χ (ε) = 320.4 nm (15200). Fluorescence (CHCl3): _{λ mdX} = 382.0 nm. Fluorescence quantum eff. (CHCl 3, standard: perylene-3,4,9,10-tetracarboxylic acid tetramethyl ester with Φ 1.00): 0.04. MS (70 eV, EI), m / z (%) = 434 (A, 100), 378 (6), 377 (16), 135 (5), 93 (4), 79 (5). HRMS (EI), m / z Ber. C E I S: 434.2102; Gef. 434.2091; _ = -1.1 mmu.

Example 8: 5,5 ^'M -di (adaraantan-l -yl) ^-2,2, 5', 2 ": 5", ^2, "-qiiaierthiophen (4b)

5- (Adamantyl-1-yl) -2,2'-dimiophene (98.7 mg, 0.328 mmol) was dissolved in chloroform (1.0 mL) and treated with iron (III) chloride (79.9 mg, 0.493 mmol). The reaction solution was stirred at room temperature (25 ° C) for 18 hours. The chloroform was removed in vacuo, the residue suspended in 2 M HCl (5 mL), stirred for 2 h and washed with 2 M HCl (100 mL) and water (20 mL). The solid was dissolved in chloroform (10 ml), filtered, the filtrate was freed from solvent and suspended in hexane-ethyl acetate 9: 1 (20 ml). After repeated filtration, the product was purified by column chromatography (silica gel, iso-hexane / chloroform 1: 1). Yield: 28.1 mg (29%) of yellow solid; M.p.> 250 ° C. IR (ATR): v = 2899, 2846, 1507, 1447, 1356. 1342, 1314, 1258, 1216, 1 183, 1 164, 1 100, 1 100, 1066, 1002, 975, 880, 826, 808, 788 684, 667 cm ^" 'UV / Vis (CHCl3):>w1; :) = 400.6 nm (31900) Fluorescence (CHCl3): / x (J _re i) ^~ 466.4 (0.98), 496.4 (1.00) fluorescence quantum yield (CHCl 3, λ _E = 400.6 nm, £ 400.6 nm / in = 0.176, standard: perylene-3,4: 9,10-tetracarboxylic acid tetramethyl ester with Φ = 1.00): 0.20 ms (70 eV, EI) , m / z (%) = 598 (Af, 100), 541 (8), 328 (5), 299 (5), 135 (1 1), HRMS (EI), m / z calc. C ₃₆ H ₃ ss4 598.1856, prepared 598.1865.

Example 9: 5,5 ' ^{, m} -Di (adamantanyl) -2,2': 5 2 '^^ (6b):

5- (Adamantyl-1-yl) -2,2 ^" : 5 ', 2" -terthiophene (18.0 mg, 0.0470 mmol) was dissolved in chloroform (0.5 mL) and treated with iron (III) chloride (1.4 mg, 0.0706 mmol). The reaction mixture was stirred for 1 h at room temperature (25 ° C) with exclusion of water (CaCl ₂ ). 1 M HCl (3 mL) was added and stirred overnight. The precipitate was filtered, suspended in ethanol and stirred for 1 h. It was repeatedly filtered and washed with ethanol (50 mL). The product was dried at 110.degree. C. for 2 days. Y. 16.2 mg (90%) of orange solid; M.p.> 250 ° C, IR (ATR) P = 3061, 2896, 2845, 1737, 1499, 1439, 1364, 1354, 1341, 1313, 1253, 1217, 1 188, 1 157, 1 100, 1070, 1001, 973, 934, 905, 876, 843, 822, 809, 787, 778, 737, 678 cm ^-1 UV / Vis (C ₂ H ₂ Cl ₄ ): Anax (ε) = 448.2 nrn (49,000). C2H2CI): Amax (A _d ) ⁼ 525.2 nm (0.98), 561.6 nm (1 .00), fluorescence quantum yield (C2H2CI4, A _Hx = 448.2 nm, E428.2 nm i cm = 0.178, standard: perylene-3,4: 9, 10-tetracarboxylic acid tetramethyl ester with Φ = 1.00): 0.20 MS (70 eV, EI), m / z (%) = 762 (AT, 100), 628 (7), 381 (11), 324 (8) HRMS (El), m / z Ber. C44H42S6 762.161 1; Well 762.1610 Elemental analysis, calc. (%) For C44H42S6 (763.2): C 69.25, H 5.55, S 25.21, Gef: C 69.79, H 5.58, S 24.66; AAS, Fe: 0.000%.

Example 10 5.5 """'- di (adamantan-l-yl) -, 5% ^2': ^5, 2 ^',': 5 ^', 2'^',': ⁵ ^', ^2, '' ^, ': 5 ^, '''% 2 ' ^, ' ^, ' ^, : 5' ^{, ,,} '2 " ^, ' ^, '' -octithiophene (8b):

5- (adamantyl-1-yl) 2,2 ': 5 \ 2 ": 5", 2 "' -quaterthiophene (42.4 mg, 0.0912 mmol) was dissolved in chloroform (1 .5 mL) and treated with iron (III) chloride (22.2mg, 0.137mmol) and the reaction mixture was stirred for 24h at room temperature (25 ° C), water (2mL) and 2M HCl (2mL) were added and stirred overnight The precipitate was filtered , suspended in ethanol, 3 h The product was dried for 1 d at 110 ° C. Yield: 43 .3 mg (98%) of a red solid, mp> 25 () ° C, IR (ATR) v = 3060, 2896, 2843. 2358, 2337, 1497, 1439, 1434, 1341, 1313, 1216, 1099, 1070, 1001. 973, 877, 842, 821, 786, 778, 736. 681, 667 cm ^"1 . UV / Vis (C2H2Cl4): 2 _m ax (ε) = 452.2 nm (64400). Fluorescence (C ₂ H ₂ Ci ₄ ): (I _K \) = 549.4 nm (1.00), 565.6 nm (0.92). Fluorescence quantum yield (C2H2CI4, = 452.2 nm, 452.2 ₁ l / cm

= 0.0859, standard: perylene-3,4: 9, 10-tetracarboxylic acid tetramethyl ester with Φ = 1.00): 0.21. MS (70 eV, EI), m / z (%) = 926 (Af, 54), 464 (24), 268 (21), 256 (22), 83 (28), 44 (100). HRMS (EI), m / z Ber. C ₅₂ H46Sg 926.1365; Gef. 926.1380; AAS, Fe: 0.007%. Example 1 1: introduction of 5- (adamantan-l-yl) -2,2 ': ^5, ^{2; ,} 5 ^" .2""- quaterthiophene (4a) into a solid PMMA matrix:

5- (Adarnantan-1-yl) -2.2 ^, 5 ', 2 " ^, 5", 2'^"'-quaterthiophene (0.972 mg) were dissolved in 32.4 g of freshly distilled methyl methacrylate. Azo-bis (isobutyronitrile). (4.90 mg) was added and stirred for 30 minutes at room temperature The solution was filtered and polymerized for 2 hours at 70 ° C. It was then polymerized at 50 ° C. for a further 4 days.

characters

Figure 1. UV / Vis spectra in chloroform with of 2a (pillared), 3a (dashed) and 4a (solid); left absorption spectra and right fluorescence spectra. Maxima from left to right: absorption of 2a. Absorbance of 3a, fluorescence of 2a, absorption of 4a, fluorescence of 3a and fluorescence of 4a.

Figure 2. UV / Vis spectra of 4a in solid PMMA matrix. Left: fluorescence excitation spectrum. Right: fluorescence spectrum.

Figure 3. Fluorescence decay curve of 4a in solid PMMA matrix. Exponential fitting (solid line) of the deconvolved measuring points gives a fluorescence lifetime of more than 36 ns.

Claims

1. Compound of formula (I):

where two radicals selected from R 1, R 2 and R 3, each of which independently represents an alkyl radical or an alkenyl radical, together with the carbon to which they are attached, may be linked to a cycloalkane radical or a cycloalkene radical which may be substituted by one or several substituents Rl 0,

or all three of R 1, R 2 and R 3, each independently an alkyl group or an alkenyl group, together with the carbon to which they are attached may be linked to a bridged cycloalkene or bridged cycloalkane group which may be substituted with one or more multiple substituents RI O;

R4 and R-5 independently of each occurrence are selected from hydrogen, F, Cl, Br, I and a linear alkyl radical having at least one and at most 37 C atoms,

wherein in the alkyl group, one to 10 CHi units may independently be replaced by each of a carbonyl group, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, an cis or rara CH = CH group in which a CH unit may also be replaced by a nitrogen atom, an acetylenic C ^ C group, a divalent phenyl radical, a divalent pyridine radical, a divalent thiophene radical, a divalent naphthalene radical in which one or two CH groups may be replaced by nitrogen atoms, a divalent anthracene radical in the one or two CH groups may be replaced by nitrogen atoms; and wherein in the alkyl radical up to 12 individual hydrogen atoms of the CH ₂ groups can each be independently replaced by the same carbon atoms by a halogen, a cyano group or a linear alkyl chain having up to 18 carbon atoms, in which one to 6 CIT units can be replaced independently of each other by a carbonyl group, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, a cis-group or an iron group. in which a CH unit may also be replaced by a nitrogen atom, an acetylenic C = C group, a divalent phenyl radical, a divalent pyridine radical, a divalent thiophene radical, a divalent naphthalene radical in which one or two CH groups may be replaced by nitrogen atoms a divalent anthracene radical in which one or two CH groups may be replaced by nitrogen atoms, and wherein up to 12 individual hydrogen atoms of the CH ₂ groups of the alkyl chain may each independently be replaced with the same C atoms by a halogen, a cyano group or a linear alkyl chain having up to 18 carbon atoms, in which one to 6 C E units may be replaced independently of each other by each a carbonyl group, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, an ice or / ra ? w-CH = CH group, in which a CH unit may also be replaced by a nitrogen atom, an acetylenic C = C group, a divalent Phe nylrest, a divalent pyridine radical, a divalent thiophene radical, a divalent naphthalene radical in which one or two CH groups may be replaced by nitrogen atoms, a divalent anthracene radical in which one or two CH groups replaced by nitrogen atoms! could be;

and wherein the free valencies of methine groups or of quaternary C atoms in such alkyl radicals may also be linked in pairs, so that a ring is formed;

R6 is selected from H and a radical C (R1 R2R3). wherein R 1, R 2 and R 3 are as defined above; n represents an integer of 2 to 12; and ni ^ηη ί IYHI en Suh ^ Htnen '^ RI O to R' f? Ι Ι ΠΠ / ΠΠΡΓ Rj inde pendently of each other are selected from F, Cl, Br, I and a linear alkyl radical as defined above for R4 and R5.

A compound according to claim 1, wherein R 6 is hydrogen.

3. A compound according to claim 1. which is a compound of formula (IIa)

wherein R4 and R5 are independently in each occurrence as defined for formula (I), n is as defined for formula (I), and R7, R8 and R9 are each independently hydrogen at each occurrence or as RI 0 for formula (I ) are defined.

4. A compound according to claim 1, which is a compound of formula (IIIa)

in which n is as defined for formula (I), and R7, R8 and R9 independently of one another at each occurrence are hydrogen or as R10 are defined for formula (I).

5. A compound according to claim 1, which is a compound of formula (IVa)

where n is as defined for formula (I).

6. A compound according to any one of claims 2 to 5, wherein n is an integer from 2 to 6, preferably from 2 to 4.

A compound according to claim 1, which is one of the following compounds 2a-4a:

4a

The compound of claim 1, wherein R 6 is -C (R 1 R 2 R 3) and R 1, R 2 and R 3 are independently defined as defined for formula (I).

Compound according to claim 1, which is a compound of formula (IIb)

in which R4 and R5 independently of one another at each occurrence are defined as for formula (I), n is as defined for formula (I), and R7, R8 and R9 independently of one another at each occurrence are hydrogen or as R10 is for formula (1) are defined.

A compound according to claim 1, which is a compound of formula (IIIb)

R9 R9 _(inb) in which n is as defined for formula (I), and R7, R8 and R9 independently of each other are hydrogen or as R10 are defined for formula (I).

11. A compound according to claim 1, which is a compound of formula (IVb)

12. A compound according to any one of claims 8 to 1 1, wherein n is an integer from 4 to 12.

] 3. A compound according to claim 1, which is one of the following compounds:

2 B

A polymer composition comprising a solid organic polymer matrix in which a compound according to any one of claims 1 to 13 is dispersed or forms a copolymer together with the polymer of the polymer matrix.

The polymer composition of claim 14, wherein the solid organic polymer matrix comprises a polymer selected from polyacrylates, poly (alkyl) acrylates, halogenated, polyacrylates, halogenated poly (alkyl) acrylates, polycyanurate, perfluorocyclobutane polymers, silicones, polycarbonates , Polystyrene, cellophane, acetylcellulose, polyfluorinated polyethers and polyfluorinated alkanes.

The polymer composition of claim 15, wherein the solid organic polymer matrix comprises a polymethylmethacrylate or polycarbonate.

17. A polymer composition according to any one of claims 14 to 16, wherein the concentration of the compound according to any one of claims 1 to 13 in the polymer matrix is in the range of 0.01 to 1000 ppm.

An optical polymer waveguide or slip ring optical system comprising a polymer composition according to any one of claims 14 to 17.

19. Use of a compound according to any one of claims 1 to 13 as a fluorescent dye in optical information collection systems, optical information processing systems or optical information transmission systems, in particular in polymer optical waveguides or optical slip ring systems.

20. Use of the polymer composition according to any one of claims 14 to 17 as a photoconductive material.

21. Use of the polymer composition according to any one of claims 14 to 17 as a photoconductive material in an optical slip ring system.

22. Use of a compound according to any one of claims 8 to 13 as a color pigment.

23. A process for the preparation of a compound according to any one of claims 1 to 13, comprising reacting an ilaiogenthiophens or a H allogeno 1 i got hi ophens with a Zinklialogenid the formula (RlR2R3) C-ZnX, wherein Rl, R2 and R3 independently as defined for the formulas in items 1 to 13 and X for Cl. Br, or I, catalyzed by a palladium compound.

24. A process for preparing a compound according to any one of claims 8 to 1 3, wherein two identical or different compounds of formula (VII)

wherein R 1 to R 5 are independently defined as in the formulas in claims 8 to 13, and r is an integer of 1 to 6 in the presence of anhydrous ferrous chloride coupled to a compound according to any one of claims 8 to 13 become.

25. Compound of formula (Vi)

wherein R 1 to R 5 are independently defined as in claim 1, X is Cl, Br or I, and q is an integer of 1 to 6.