CA1255686A - (2-fluoro-5,6,11,12-tetraselenotetracene).sub.2 chloride, process for its preparation and its use - Google Patents
(2-fluoro-5,6,11,12-tetraselenotetracene).sub.2 chloride, process for its preparation and its useInfo
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Abstract
(2-Fluoro-5,6,11,12-tetraselenotetracene)2 chloride, process for its preparaton and its use.
Abstract The novel complex of the formula I
(I) is an organic material with a high electrical conductivity and with a metallic phase transition at about 125°K under normal pressure, at which the conductivity increases suddenly.
The complex can be used, for example, as an organic electrical conductor.
Abstract The novel complex of the formula I
(I) is an organic material with a high electrical conductivity and with a metallic phase transition at about 125°K under normal pressure, at which the conductivity increases suddenly.
The complex can be used, for example, as an organic electrical conductor.
Description
~:~5`5~3~3~
6-14767/=
(2~Fluoro-5,6,11,12-tetraselenotetracene)2 chloride, process for its pre~aration and it5 use. ___ __ The invention relates to t2-fluoro 5,6,11,12-tetra-selenotetracene)2 chloride, a process for its preparation and its use in information systems or electronic components.
Various mechanically conductive chalcogenated tetra-cene complexes, for example t5,6,11,12-tetraselenotetracene)2 iodide, bromide or chloride or (5,6,11,12-tetrathiotetra-cene)2tiodine)3, are known from the l;terature~ These com-plexes exhibit a relatively sharp transition from themetallic to the non-conductive state at temperatures between about 30 and 45 K, i~e. the metallic phase of these complexes is not stable down to sufficiently low temperatures at which, for example, superconductivity can be expected. It is also known that the transition point from the metallic to the non-conductive state in the ttetrathiotetracene)2(iodine)3 com-plex can be reduced under pressure or by changing the stoi-chiometry tincreasing the iodine concentration above the 2:3 ratio). It is assumed that the stabilisation of the metallic phase in complexes which deviat~e from the exact 2:3 stoichio-metry is caused by a change in the occupation of the bands~
The mechanism which causes the stabilisation of the metallic phase of the above complexes under the influence of pressure is still largely unknown. No complexes based on 5,6,11,12-tetrathiotetracene or -tetraselenotetracene halides which exhibit a metallic phase transition only as a result of a change in temperature and without the influence of pressure have yet been d;sclosed.
The present invention relates to a complex of the ~;
. , , .
8~
formula I
Sc Se (3 ~I) ~ F Cl(~) i i1 \0~, S~Se 2 which~ surprisingly and in contrast~ for example, to the abovementioned (tetraselenotetracene)2-iodine, -bromine or 5 -chlorine complexes, is distinguished by a stable metallic phase down to at least S K under normal pressure, i.e. the electrical conductivity of the complex increases from room temperature (20-25C) down to at least 5K. Moreover, a marked jump in the increase in the conductivity is observed 10 at about 125 K. The complex of the formula I exhibits an electrical conductivity ~] of up to 1,200 ohm~1 cm~1 at room temperature and an electrical conductivity of 7,000 ohm 1 cm 1 at S K (measured around the preferred direction of growth =
axis of the needle). At 125 K, the conductivity ir,creases 15 suddenly by a factor of 2.6 The complex according to the invention contains the space group P2/n. The length of the axes of the unit cells are: a = 1.7492 nm, b = 0 5159 nm and c = 1.7486 nm. The complex is monoclinical and, in addition to the high elec-20 trical conductivity, also has ~a pronounced electrical andoptical anisotropy. The complex according to the invention can be, for example, in the form of microcrystalline powders, as an amorphous layer, as a layer of microcrystals~ as an amorphous 25 powder or in the form of monocrystals, and can be used as an electrical conductor.
Figure 1 shows a projection of the crystal structure of the complex according to the invention.
The complex of the formula I can be prepared by ., .
~i~55t~
" .
~ 3 var;ous methods, for example by (direct) oxidation of 2-fluoro-5,6,11,12-tetraselenotetracene with chlorine or an oxidising chlorine salt which splits off chlorine, such as copper(II) chloride and FeCl3, in the presence of an inert organic solvent. Examples of suitable inert organic solvents are halogenated aliphatic hydrocarbons, such as methylene chloride and 1,1,2-trichloroethane; polar substituted, in particular halogenated, aromatic hydrocarbons, such as chloro-benzene, o-dichlorobenzene, 1,2,3-trichloroben~ene~ 1,Z,4-trichlorobenzene and chlorinated naphthalenes; other poLarsolvents, such as benzonitrile and alkylnitriles with 2-5 C
atoms, for example acetonitrile, propionitrile and butyro-nitrile; nitrobenzene; N,N-dialkylamides of aliphatic mono-carboxylic acids with 1-4 C atoms in the acid part, for example N,N-dimethylformamide and N,N-dimethylacetamide;
N,N,N',N'-tetramethylurea; dialkylsulfoxides, such as dimethylsulfoxide and diethylsulfoxide; and cyclic ethers, such as tetrahydropyran, tetrahydrofuran and dioxane. Mix-tures of the solvents mentioned can also be used. The reac-; 20 tion temperatures in these oxidation reactions are in general between 20 and 120C.
The complex of the formula I can also be prepared bydiffusion of chlorine from the gas phase or from a carrier solution into a solution of 2-fluoro-5,6,11,12-tetraseleno-tetracene, possible solvents being those of the abovementionedtype.
The complex of the formula I can furthermore be pre-pared from the gas phase, i.e.`by cosublimation of 2-fluoro-5,6,11,12-tetraselenotracene and chlorine by a process analo-gous to that described in 6erman Patent Specification2~641~742. In this Process~ the 2-fluoro-5,6,11,12-tetra-selenotetracene and the chlorine are advantageously allowed to react with one another in an inert gas atmosphere, pre-` ferably in an open system. ~lowever, the reaction in the gas phase can also be carried out in a closed sys~em in aninert gas atmosphere. The reac~ion in the gas phase can be carried out, for example9 by bringing chlorine gas into . . ~
contact with 2-fluoro-5,6,11,12 tetraselenotetracene by means of an inert carrier gas in the gas phase at about 260C. In this procedure, the crystals grow in the desired form, for example in the form of rods or tubes, on the reactor walls andtor any substrate which may be located in the reactor, such as aluminium oxide or, preferably, quartz. The carrier gases which are used in this preparation method are advantageously highly pure ;nert gases, such as argon, nitrogen, helium and xenon. The reaction temperatures in the gas phase reaction are advantageously between 180 and 300C. The crystals obtained by a gas phase reaction can easily be removed from the reaction chamber or from the substrate~ A suitable experi-mental design for this preparation method is described in the abovementioned German Patent Specification 2,641,742.
Preferably, however, the complex according to the invention is prepared by electrochemical oxidation of 2-fluoro-5,6,11,12-tetraselenotetracene in the presence of an inert organic solvent and a chloride-containing conductive salt~ Inert organic solvents which can be used are those of the abovementioned type~ Preferred solvents are cyclic ethers and N,N-dialkylamides of aliphatic monocarboxylic acids or mixtures thereof, in particular tetrahydroFuran and N,N-dimethylformamide or mixtures thereof. Examples of suitable chloride-containing conductive salts are salts of the formula II
R ~Y-R Cl ~ (II) in which Y is N, P or As and R1 to R4 independently of one another are C1_18-alkyl, benzyl, phenyl or naphthyl Alkyl groups R1 to R4 can be straight-chain or branched and pre-ferably contain 1-12 C atoms. Examples of such alkyl groups are: methyl, ethyl, n-propyl, isopropyl, n~butyl, sec.-butyl, tert.-butyl, 1,1,3,3 tetramethylbutyl, n-pentyl, ~556~3~
6-14767/=
(2~Fluoro-5,6,11,12-tetraselenotetracene)2 chloride, process for its pre~aration and it5 use. ___ __ The invention relates to t2-fluoro 5,6,11,12-tetra-selenotetracene)2 chloride, a process for its preparation and its use in information systems or electronic components.
Various mechanically conductive chalcogenated tetra-cene complexes, for example t5,6,11,12-tetraselenotetracene)2 iodide, bromide or chloride or (5,6,11,12-tetrathiotetra-cene)2tiodine)3, are known from the l;terature~ These com-plexes exhibit a relatively sharp transition from themetallic to the non-conductive state at temperatures between about 30 and 45 K, i~e. the metallic phase of these complexes is not stable down to sufficiently low temperatures at which, for example, superconductivity can be expected. It is also known that the transition point from the metallic to the non-conductive state in the ttetrathiotetracene)2(iodine)3 com-plex can be reduced under pressure or by changing the stoi-chiometry tincreasing the iodine concentration above the 2:3 ratio). It is assumed that the stabilisation of the metallic phase in complexes which deviat~e from the exact 2:3 stoichio-metry is caused by a change in the occupation of the bands~
The mechanism which causes the stabilisation of the metallic phase of the above complexes under the influence of pressure is still largely unknown. No complexes based on 5,6,11,12-tetrathiotetracene or -tetraselenotetracene halides which exhibit a metallic phase transition only as a result of a change in temperature and without the influence of pressure have yet been d;sclosed.
The present invention relates to a complex of the ~;
. , , .
8~
formula I
Sc Se (3 ~I) ~ F Cl(~) i i1 \0~, S~Se 2 which~ surprisingly and in contrast~ for example, to the abovementioned (tetraselenotetracene)2-iodine, -bromine or 5 -chlorine complexes, is distinguished by a stable metallic phase down to at least S K under normal pressure, i.e. the electrical conductivity of the complex increases from room temperature (20-25C) down to at least 5K. Moreover, a marked jump in the increase in the conductivity is observed 10 at about 125 K. The complex of the formula I exhibits an electrical conductivity ~] of up to 1,200 ohm~1 cm~1 at room temperature and an electrical conductivity of 7,000 ohm 1 cm 1 at S K (measured around the preferred direction of growth =
axis of the needle). At 125 K, the conductivity ir,creases 15 suddenly by a factor of 2.6 The complex according to the invention contains the space group P2/n. The length of the axes of the unit cells are: a = 1.7492 nm, b = 0 5159 nm and c = 1.7486 nm. The complex is monoclinical and, in addition to the high elec-20 trical conductivity, also has ~a pronounced electrical andoptical anisotropy. The complex according to the invention can be, for example, in the form of microcrystalline powders, as an amorphous layer, as a layer of microcrystals~ as an amorphous 25 powder or in the form of monocrystals, and can be used as an electrical conductor.
Figure 1 shows a projection of the crystal structure of the complex according to the invention.
The complex of the formula I can be prepared by ., .
~i~55t~
" .
~ 3 var;ous methods, for example by (direct) oxidation of 2-fluoro-5,6,11,12-tetraselenotetracene with chlorine or an oxidising chlorine salt which splits off chlorine, such as copper(II) chloride and FeCl3, in the presence of an inert organic solvent. Examples of suitable inert organic solvents are halogenated aliphatic hydrocarbons, such as methylene chloride and 1,1,2-trichloroethane; polar substituted, in particular halogenated, aromatic hydrocarbons, such as chloro-benzene, o-dichlorobenzene, 1,2,3-trichloroben~ene~ 1,Z,4-trichlorobenzene and chlorinated naphthalenes; other poLarsolvents, such as benzonitrile and alkylnitriles with 2-5 C
atoms, for example acetonitrile, propionitrile and butyro-nitrile; nitrobenzene; N,N-dialkylamides of aliphatic mono-carboxylic acids with 1-4 C atoms in the acid part, for example N,N-dimethylformamide and N,N-dimethylacetamide;
N,N,N',N'-tetramethylurea; dialkylsulfoxides, such as dimethylsulfoxide and diethylsulfoxide; and cyclic ethers, such as tetrahydropyran, tetrahydrofuran and dioxane. Mix-tures of the solvents mentioned can also be used. The reac-; 20 tion temperatures in these oxidation reactions are in general between 20 and 120C.
The complex of the formula I can also be prepared bydiffusion of chlorine from the gas phase or from a carrier solution into a solution of 2-fluoro-5,6,11,12-tetraseleno-tetracene, possible solvents being those of the abovementionedtype.
The complex of the formula I can furthermore be pre-pared from the gas phase, i.e.`by cosublimation of 2-fluoro-5,6,11,12-tetraselenotracene and chlorine by a process analo-gous to that described in 6erman Patent Specification2~641~742. In this Process~ the 2-fluoro-5,6,11,12-tetra-selenotetracene and the chlorine are advantageously allowed to react with one another in an inert gas atmosphere, pre-` ferably in an open system. ~lowever, the reaction in the gas phase can also be carried out in a closed sys~em in aninert gas atmosphere. The reac~ion in the gas phase can be carried out, for example9 by bringing chlorine gas into . . ~
contact with 2-fluoro-5,6,11,12 tetraselenotetracene by means of an inert carrier gas in the gas phase at about 260C. In this procedure, the crystals grow in the desired form, for example in the form of rods or tubes, on the reactor walls andtor any substrate which may be located in the reactor, such as aluminium oxide or, preferably, quartz. The carrier gases which are used in this preparation method are advantageously highly pure ;nert gases, such as argon, nitrogen, helium and xenon. The reaction temperatures in the gas phase reaction are advantageously between 180 and 300C. The crystals obtained by a gas phase reaction can easily be removed from the reaction chamber or from the substrate~ A suitable experi-mental design for this preparation method is described in the abovementioned German Patent Specification 2,641,742.
Preferably, however, the complex according to the invention is prepared by electrochemical oxidation of 2-fluoro-5,6,11,12-tetraselenotetracene in the presence of an inert organic solvent and a chloride-containing conductive salt~ Inert organic solvents which can be used are those of the abovementioned type~ Preferred solvents are cyclic ethers and N,N-dialkylamides of aliphatic monocarboxylic acids or mixtures thereof, in particular tetrahydroFuran and N,N-dimethylformamide or mixtures thereof. Examples of suitable chloride-containing conductive salts are salts of the formula II
R ~Y-R Cl ~ (II) in which Y is N, P or As and R1 to R4 independently of one another are C1_18-alkyl, benzyl, phenyl or naphthyl Alkyl groups R1 to R4 can be straight-chain or branched and pre-ferably contain 1-12 C atoms. Examples of such alkyl groups are: methyl, ethyl, n-propyl, isopropyl, n~butyl, sec.-butyl, tert.-butyl, 1,1,3,3 tetramethylbutyl, n-pentyl, ~556~3~
2-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl and n-octadecyl. Compounds of the formula II in which Y is N or P, R1 iS benzyl or phenyl and R2 to R4 are straight-chain alkyl with in each case 1-12 C
atoms or phenyl, or R1 and R4 are straight-chain alkyl with in each case 1-12 C atoms, are preferably used~ Compounds of the formula II in which Y is N and R1 to R4 are straight-chain alkyl with in each case 1-12 C atoms, and in particular in each case n-hexyl, are particularly preferred.
Between 0~01 and 30 9 of conductive salt per litre are advantageously used, depending on the temperature of the electrolysis cell and the solvent employed~ Devices which are known per se can be used as the electrolysis cells, for example those in which the anode chamber is separated from the cathode chamber by a Teflon screen, glass frits or capillariesO The dimensions of the electrolysis cells can vary depending on the amount of reaction components used, and have virtually no adverse effect on the quality of the result-ing complex of the formula Io Cell volumes of, for example, 15-10û ml are particularly suitable for the preparation of about 5-50 mg of complex of the formula I.
The reaction temperatures (temperatures of the elec-trolysis cells) are advantageously between 0 and 120C, depending on the nature of the solvent used. The current strength in general varies between 0.005 /uA and 5 luA~ The diameter of the anodes and cathodes is advantageously between 0.1 and 5 mm.
In the above reactions~, at least stoichiometric amounts of the 2-fluoro-5,6,11,12-tetraselenotetracene and chlorine or chloride salt are employed~ However, it is generally advisable to start with an excess of chlorine or chloride salt, so that there is a 20-fold to 1,000-fold molar excess of chlorine or chloride salt in the reaction phase at any time~
2-(Fluoro)-5,6,11,12-tetraselenotetracene (formula VI) can be obtained via the intermediates of the formulae III to V
~2~5~
~ 9~ COOH
O
~ (IV) ~
O
Xl X
t11 t I i (v) and , ~./-\,~\
X X
Se-Se (VI), Se-Se in which the symbols X1 and X are each hydrogen or the symbols X1 are each hydrogen and the symbols X are each chlorine or the symbols X1 are each chlorine and the symbols X are each hydrogen~ ~
The compounds of the formulae III to VI can be pre-pared by processes which are analogous to those which are known per se, by reacting 2,3-naphthalenedicarboxylic anhy-dride with fluorobenzene in the presence of a Friedel Crafts catalyst, preferably aluminium chloride, to give the compound of the formula III, cyclising the Z-t4-fluorobenzoyl)-naphtha-lene-3-carboxylic ac-id to give 2-fluoro-5,12-naphthacene-quinone (compound of the formula IV), reducing the compound of the formula IV to give 2-fluorotetracene (compound of the ~25~
formula V where X1 and X = H), for example in the presence of zinc dust in an acid medium, for example acetic acid, reacting the 2-fluorotetracene with sulfuryl chloride to give 2-fluoro-5,11- or 2-fluoro-6,12-dichlorotetracene ~c f, for 5 example, Bull. Soc. Chim. France, 427 (1~4û)], and, finally, react;ng the 2-fluoro-5,11- or 2-fluoro~6,12-dichlorotetra-cene or a mixture thereof with selenium at elevated tempera-ture.
The cyclisation of the 2-(3-fluorobenzoyl)-naphtha-10 lene-3-carboxylis acid to give 2-fluoro-5~12-naphthacene-quinone can be carried out in a manner which is known per se in the presence of a proton acid or a Lewis acid. Examples of suitable proton acids are polyphosphoric acid, chloro-sulfonic acid and sulfuric acid. Examples of possible Lewis 15 ac;ds are boron tr;fluor;de and, ;n particular, aluminium tr;chloride. Cyclisation ;n the presence of a Lewis acid, in particular aluminium chloride, in the melt is preferred. The reaction of the S-fluorotetracene with sulfuryl chloride and the reaction oF the 2-fluoro-5,11- or 2-fluoro-6,12-dichloro-20 tetracene w;th selen;um are advantageously carried out in the presence of an inert organic solvent. Suitable solvents for the reaction of the 2-fluorotetracene with sulfuryl chloride are, for example, nitrobenzene~ benzene and carbon tetra-chloride. N;trobenzene is the preferred solvent.
The react;on of the 2-fluoro-5,11- or 2-fluoro-6,12-d;chlorotetracene ;s preferably carr;ed out in the presence of a halogenated aromatic hydrocarbon, in particular 1,2,4-trichlorobenzene.
On the basis of the mechanically electrical con-30 ductivity and the marked electrical and optical anisotropy, the complex according to the invention is suitable ~for use as an organic electrical conductor, for example for conductive coatings on plastic fibres; and furthermore as a polariser mater;al or as an additive to antistatic coatings and cover-35 ings, for example those based on plastic~ The complex of the formula I can also be employed in highly conductive printing materials or processes which are sensitive ~owards electron ~:~5~;6~3~
beams or are photosènsitive, such as those described, for example, in European Patent Application Publication No.
23,988 and U.S. Patent Specification 4~036,648. Due to its redox properties and the var;ous intensive colours of its redox stages (green, blue-green, blue and yellow), the com-plex of the formula I can furthermore be advantageously used in information systems, such as colour display screens, and in electronic components~ The highLy conductive complex of the formula I is Particularly suitable for this purpose, since it can be subjected to further oxidation and reduction in electrical arrangements, such as, for example, electrochromic circuits~ However, on the basis of its metallic phase, which is stable down to about 5 K~ the complex according to the invention is particularly suitable for various uses in low temperature technology, for example For use as an electrically conductive layer in capacitor films or as cathode material in solid electrolyte cells~ which can thus also be used at a low temperature. The complex can furthermore be used for pressure-and/or temperature-dependent circuit elements or for circuit elements which depend on a magnetic field.
Example __ . ___ a) ~5.0 9 ~227 mmol) of 2,3-naphthalenedicarboxylic acid anhydride are suspended in 200 ml (2.1 moles) of fluoro-benzene. 75.5 9 ~565 mmol) of powdered aluminium chloride are added in the course of 5 minutes, with vigorous stirring (exothermic reaction up to about 320C)A The dark red suspen-sion is refluxed and stirred for 6 hours. The solution is then allowed to cool to room t~emperature and is poured onto about 500 9 of ice, and is stirred to bring the hydrolysis to completion~ Excess fluorobenzene is evaporated off and the resulting praduct is suspended in water. The suspension is filtered, the filtrate is rinsed with water and the product is dried. 76 9 of crude Z~ fluorobenzoyl)-naphthalene-3-carboxylic acid are obtained. The crude product is stirred with 2 litres of 10% sodium carbonate solution, the resulting solution is acidified with hydrochloric acid and the white precipitate is filtered off and dried. 54~2 9 (81Z of ~25~
theory) of 2-(4-fluorobenzoyl)-rlaphthalene-3-carboxylic acid are obtained.
Mass spectrum: (M+ = 294; M~-COOH = 249, M+-COO = 250, M+-C6H4F = 199);
IR spectrum (KBr): OH about 3,300 cm 1; C~O double band 1,695/1,705 cm 1 b) 200 9 (1.5 moles) of powdered aluminium chloride and 40 9 (684 mmol) of sodium chloride are heated together at 140-150C~ After about 105 hours, 40 9 (136 mmol) of 2-(4-fluorobenzoyl) naphthalene-3-carboxylic acid are added to the melt. The dark red mixture is stirred at 140 150C for one hour. Hydrolysis is then carried out at about 100C by slowly adding ice-water~ The precip;tate is filtered off and stirred with 10% sodium carbonate solution~ It is then washed neutral with water and dried. The resulting product is sublimed at 230~ 13.1 9 (7û% of theory) of 2-fluoro-5,12-naphthacenequ;none are obtained.
Thin layer chromatography: silica gel, benzene: Rx ~0.6;
yellow fluorescent spot.
NMR (100 MHz in C~Cl3): multiplet which is complicated but can be interpreted, in the aromatic region.
Mass spectrum: M+ = 276, M+-CO= 248, M~-2CO = 220.
c) 8.0 g t29 mmol) of 2-fluoro-5,12-naphthacenequinone, 40 ml of water, 680 ml of acetic acid and 40 9 (611 mmol) of zinc dust are brought together and refluxed. After refluxing for 30 minutes, with stirring, the mixture is cooled and 200 ml of water are added. The resulting suspension of 2-fluorotetracene is decanted of~f, the zinc dust remaining in the flask. The 2-fluorotetracene is filtered off, washed w;th water and ethanol and dried. After recrystallisation from 500 ml of xylene, 4.0 9 ~56% of theory) of 2-f`luoro-tetracene are obtained.
UV tbenzene): typical tetracene spectrum. ~max 476, 446, 420 and 394 nm~
Mass spectrum: M~ = 246, M+2 = 123.
d) 5.0 g (20.3 mmol) of 2~fluorotetracene are suspended in 25 ml of nitrobenzene, under nitrogen, and the suspension ~255Çi~
is cooled to 5C. 5.9 9 (43.7 mmol) of sulfuryl chloride in 25 ml of nitrobenzene are then added dropwise in the course of 30 minutes and the mixture is stirred at 5C for 2 hours. The temPerature is then allowed to rise to 20-25C
and the mixture is heated to 90C in the course of 1.5 hours, stirred at this temperature for 10 minutes and cooled. The suspension is filtered off, rinsed with about 600 ml of ethanol and dried. 5.0 9 (78% of theory) of 2-fluoro-5,11-or 6,12-dichlorotetracene are obtained.
Mass spectrum: M~ = 314/316 (~ 2 Cl), M~-HCl ~ 2~8, M~-2Cl = 244, M~2 = 157/158 (2 Cl).
e) 7.2 9 (22.~ mmol) of 2-fluoro-5,11-dichLorotetracene, 7.7 9 (97.5 ~mol) of selenium and 175 ml of trichlorobenzene are brought together and are refluxed at a bath temperature of 250C under nitrogen for 120 hours. After 70 hours, a further 3~8 9 (48.1 mmol) of selenium are added. The sus-pension is then allowed to cool and is diluted with about 20û ml of n-hexane and filtered. The product is rinsed with benzene and n-hexane and dried, and is then sublirned under a high vacuum at 260-270C/10 3 bar. 4.4 9 (35% of theory) of 2-fluoro-5,6,11,12-tetraselenotetracene are obtained.
UV spectrum in trichlorobenzene: ~ max = 719, 659 and 466 nm.
f) 30 mg of 2-fluoro-5,6,11,12-tetraselenotetracene are introduced into the anode chamber of an electrolysis cell with a volume of 40 ml~ 60 mg of tetra-n-hexyl-ammonium chloride are added as a conductive salt. The cell is evacuated under 5 x 10 2 mbar overnight in a drying cabinet and is flushed with argon. 33 ml of a mixture of 25% by volume of chloro-benzene and 75% by volume of N,N-dimethylformamide are then added as the solvent~ After the mixture has been heated up to 90C for 4 hours, the cell ;s placed under a voltage of 0~1 volt for 1 hour; this voltage is increased to 0.4 volt in 3 stages in the course of 2 days, an electrolysis current of 1.06 juA being established. After 8 days, the crystals formed at the anode (diameter 1 mm; ~0% by weight of Pt, 20% by weight of IR) are detached by washing off with ethanol.
Four crystals with average dimensions of 4 mm x 40 ~m x 40 /um - ~S5686 are mounted on 4 probes consisting of gold wires 25 ~m thick by means of platinum paste (Pt paste 308 from Degussa) The conductivity of the crystals at room temperature, measured in the above probe arrangement, var;es from 700 to 1,200 ohm 1 cm 1 The temperature-dependency of the specific resistance, standardised to 295 K, shows, for all the crystals, the behaviour shown in Figure 1, within a measurement accuracy of 2%.
atoms or phenyl, or R1 and R4 are straight-chain alkyl with in each case 1-12 C atoms, are preferably used~ Compounds of the formula II in which Y is N and R1 to R4 are straight-chain alkyl with in each case 1-12 C atoms, and in particular in each case n-hexyl, are particularly preferred.
Between 0~01 and 30 9 of conductive salt per litre are advantageously used, depending on the temperature of the electrolysis cell and the solvent employed~ Devices which are known per se can be used as the electrolysis cells, for example those in which the anode chamber is separated from the cathode chamber by a Teflon screen, glass frits or capillariesO The dimensions of the electrolysis cells can vary depending on the amount of reaction components used, and have virtually no adverse effect on the quality of the result-ing complex of the formula Io Cell volumes of, for example, 15-10û ml are particularly suitable for the preparation of about 5-50 mg of complex of the formula I.
The reaction temperatures (temperatures of the elec-trolysis cells) are advantageously between 0 and 120C, depending on the nature of the solvent used. The current strength in general varies between 0.005 /uA and 5 luA~ The diameter of the anodes and cathodes is advantageously between 0.1 and 5 mm.
In the above reactions~, at least stoichiometric amounts of the 2-fluoro-5,6,11,12-tetraselenotetracene and chlorine or chloride salt are employed~ However, it is generally advisable to start with an excess of chlorine or chloride salt, so that there is a 20-fold to 1,000-fold molar excess of chlorine or chloride salt in the reaction phase at any time~
2-(Fluoro)-5,6,11,12-tetraselenotetracene (formula VI) can be obtained via the intermediates of the formulae III to V
~2~5~
~ 9~ COOH
O
~ (IV) ~
O
Xl X
t11 t I i (v) and , ~./-\,~\
X X
Se-Se (VI), Se-Se in which the symbols X1 and X are each hydrogen or the symbols X1 are each hydrogen and the symbols X are each chlorine or the symbols X1 are each chlorine and the symbols X are each hydrogen~ ~
The compounds of the formulae III to VI can be pre-pared by processes which are analogous to those which are known per se, by reacting 2,3-naphthalenedicarboxylic anhy-dride with fluorobenzene in the presence of a Friedel Crafts catalyst, preferably aluminium chloride, to give the compound of the formula III, cyclising the Z-t4-fluorobenzoyl)-naphtha-lene-3-carboxylic ac-id to give 2-fluoro-5,12-naphthacene-quinone (compound of the formula IV), reducing the compound of the formula IV to give 2-fluorotetracene (compound of the ~25~
formula V where X1 and X = H), for example in the presence of zinc dust in an acid medium, for example acetic acid, reacting the 2-fluorotetracene with sulfuryl chloride to give 2-fluoro-5,11- or 2-fluoro-6,12-dichlorotetracene ~c f, for 5 example, Bull. Soc. Chim. France, 427 (1~4û)], and, finally, react;ng the 2-fluoro-5,11- or 2-fluoro~6,12-dichlorotetra-cene or a mixture thereof with selenium at elevated tempera-ture.
The cyclisation of the 2-(3-fluorobenzoyl)-naphtha-10 lene-3-carboxylis acid to give 2-fluoro-5~12-naphthacene-quinone can be carried out in a manner which is known per se in the presence of a proton acid or a Lewis acid. Examples of suitable proton acids are polyphosphoric acid, chloro-sulfonic acid and sulfuric acid. Examples of possible Lewis 15 ac;ds are boron tr;fluor;de and, ;n particular, aluminium tr;chloride. Cyclisation ;n the presence of a Lewis acid, in particular aluminium chloride, in the melt is preferred. The reaction of the S-fluorotetracene with sulfuryl chloride and the reaction oF the 2-fluoro-5,11- or 2-fluoro-6,12-dichloro-20 tetracene w;th selen;um are advantageously carried out in the presence of an inert organic solvent. Suitable solvents for the reaction of the 2-fluorotetracene with sulfuryl chloride are, for example, nitrobenzene~ benzene and carbon tetra-chloride. N;trobenzene is the preferred solvent.
The react;on of the 2-fluoro-5,11- or 2-fluoro-6,12-d;chlorotetracene ;s preferably carr;ed out in the presence of a halogenated aromatic hydrocarbon, in particular 1,2,4-trichlorobenzene.
On the basis of the mechanically electrical con-30 ductivity and the marked electrical and optical anisotropy, the complex according to the invention is suitable ~for use as an organic electrical conductor, for example for conductive coatings on plastic fibres; and furthermore as a polariser mater;al or as an additive to antistatic coatings and cover-35 ings, for example those based on plastic~ The complex of the formula I can also be employed in highly conductive printing materials or processes which are sensitive ~owards electron ~:~5~;6~3~
beams or are photosènsitive, such as those described, for example, in European Patent Application Publication No.
23,988 and U.S. Patent Specification 4~036,648. Due to its redox properties and the var;ous intensive colours of its redox stages (green, blue-green, blue and yellow), the com-plex of the formula I can furthermore be advantageously used in information systems, such as colour display screens, and in electronic components~ The highLy conductive complex of the formula I is Particularly suitable for this purpose, since it can be subjected to further oxidation and reduction in electrical arrangements, such as, for example, electrochromic circuits~ However, on the basis of its metallic phase, which is stable down to about 5 K~ the complex according to the invention is particularly suitable for various uses in low temperature technology, for example For use as an electrically conductive layer in capacitor films or as cathode material in solid electrolyte cells~ which can thus also be used at a low temperature. The complex can furthermore be used for pressure-and/or temperature-dependent circuit elements or for circuit elements which depend on a magnetic field.
Example __ . ___ a) ~5.0 9 ~227 mmol) of 2,3-naphthalenedicarboxylic acid anhydride are suspended in 200 ml (2.1 moles) of fluoro-benzene. 75.5 9 ~565 mmol) of powdered aluminium chloride are added in the course of 5 minutes, with vigorous stirring (exothermic reaction up to about 320C)A The dark red suspen-sion is refluxed and stirred for 6 hours. The solution is then allowed to cool to room t~emperature and is poured onto about 500 9 of ice, and is stirred to bring the hydrolysis to completion~ Excess fluorobenzene is evaporated off and the resulting praduct is suspended in water. The suspension is filtered, the filtrate is rinsed with water and the product is dried. 76 9 of crude Z~ fluorobenzoyl)-naphthalene-3-carboxylic acid are obtained. The crude product is stirred with 2 litres of 10% sodium carbonate solution, the resulting solution is acidified with hydrochloric acid and the white precipitate is filtered off and dried. 54~2 9 (81Z of ~25~
theory) of 2-(4-fluorobenzoyl)-rlaphthalene-3-carboxylic acid are obtained.
Mass spectrum: (M+ = 294; M~-COOH = 249, M+-COO = 250, M+-C6H4F = 199);
IR spectrum (KBr): OH about 3,300 cm 1; C~O double band 1,695/1,705 cm 1 b) 200 9 (1.5 moles) of powdered aluminium chloride and 40 9 (684 mmol) of sodium chloride are heated together at 140-150C~ After about 105 hours, 40 9 (136 mmol) of 2-(4-fluorobenzoyl) naphthalene-3-carboxylic acid are added to the melt. The dark red mixture is stirred at 140 150C for one hour. Hydrolysis is then carried out at about 100C by slowly adding ice-water~ The precip;tate is filtered off and stirred with 10% sodium carbonate solution~ It is then washed neutral with water and dried. The resulting product is sublimed at 230~ 13.1 9 (7û% of theory) of 2-fluoro-5,12-naphthacenequ;none are obtained.
Thin layer chromatography: silica gel, benzene: Rx ~0.6;
yellow fluorescent spot.
NMR (100 MHz in C~Cl3): multiplet which is complicated but can be interpreted, in the aromatic region.
Mass spectrum: M+ = 276, M+-CO= 248, M~-2CO = 220.
c) 8.0 g t29 mmol) of 2-fluoro-5,12-naphthacenequinone, 40 ml of water, 680 ml of acetic acid and 40 9 (611 mmol) of zinc dust are brought together and refluxed. After refluxing for 30 minutes, with stirring, the mixture is cooled and 200 ml of water are added. The resulting suspension of 2-fluorotetracene is decanted of~f, the zinc dust remaining in the flask. The 2-fluorotetracene is filtered off, washed w;th water and ethanol and dried. After recrystallisation from 500 ml of xylene, 4.0 9 ~56% of theory) of 2-f`luoro-tetracene are obtained.
UV tbenzene): typical tetracene spectrum. ~max 476, 446, 420 and 394 nm~
Mass spectrum: M~ = 246, M+2 = 123.
d) 5.0 g (20.3 mmol) of 2~fluorotetracene are suspended in 25 ml of nitrobenzene, under nitrogen, and the suspension ~255Çi~
is cooled to 5C. 5.9 9 (43.7 mmol) of sulfuryl chloride in 25 ml of nitrobenzene are then added dropwise in the course of 30 minutes and the mixture is stirred at 5C for 2 hours. The temPerature is then allowed to rise to 20-25C
and the mixture is heated to 90C in the course of 1.5 hours, stirred at this temperature for 10 minutes and cooled. The suspension is filtered off, rinsed with about 600 ml of ethanol and dried. 5.0 9 (78% of theory) of 2-fluoro-5,11-or 6,12-dichlorotetracene are obtained.
Mass spectrum: M~ = 314/316 (~ 2 Cl), M~-HCl ~ 2~8, M~-2Cl = 244, M~2 = 157/158 (2 Cl).
e) 7.2 9 (22.~ mmol) of 2-fluoro-5,11-dichLorotetracene, 7.7 9 (97.5 ~mol) of selenium and 175 ml of trichlorobenzene are brought together and are refluxed at a bath temperature of 250C under nitrogen for 120 hours. After 70 hours, a further 3~8 9 (48.1 mmol) of selenium are added. The sus-pension is then allowed to cool and is diluted with about 20û ml of n-hexane and filtered. The product is rinsed with benzene and n-hexane and dried, and is then sublirned under a high vacuum at 260-270C/10 3 bar. 4.4 9 (35% of theory) of 2-fluoro-5,6,11,12-tetraselenotetracene are obtained.
UV spectrum in trichlorobenzene: ~ max = 719, 659 and 466 nm.
f) 30 mg of 2-fluoro-5,6,11,12-tetraselenotetracene are introduced into the anode chamber of an electrolysis cell with a volume of 40 ml~ 60 mg of tetra-n-hexyl-ammonium chloride are added as a conductive salt. The cell is evacuated under 5 x 10 2 mbar overnight in a drying cabinet and is flushed with argon. 33 ml of a mixture of 25% by volume of chloro-benzene and 75% by volume of N,N-dimethylformamide are then added as the solvent~ After the mixture has been heated up to 90C for 4 hours, the cell ;s placed under a voltage of 0~1 volt for 1 hour; this voltage is increased to 0.4 volt in 3 stages in the course of 2 days, an electrolysis current of 1.06 juA being established. After 8 days, the crystals formed at the anode (diameter 1 mm; ~0% by weight of Pt, 20% by weight of IR) are detached by washing off with ethanol.
Four crystals with average dimensions of 4 mm x 40 ~m x 40 /um - ~S5686 are mounted on 4 probes consisting of gold wires 25 ~m thick by means of platinum paste (Pt paste 308 from Degussa) The conductivity of the crystals at room temperature, measured in the above probe arrangement, var;es from 700 to 1,200 ohm 1 cm 1 The temperature-dependency of the specific resistance, standardised to 295 K, shows, for all the crystals, the behaviour shown in Figure 1, within a measurement accuracy of 2%.
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. The complex of the formula I
(I)
(I)
2. A process for the preparation of the complex of the formula I according to claim 1, which comprises oxidising 2-fluoro-5,6,11,12-tetraselenotetracene with chlorine or with an oxidising chlorine salt which splits off chlorine, in the presence of an inert solvent.
3. The process according to claim 2, wherein the oxida-tion is carried out with chlorine in the gas phase.
4. The process according to claim 2, wherein the oxida-tion is carried out electrochemically in the presence of a chloride-containing conductive salt in an inert solvent.
5. The process according to claim 4, wherein a compound of the formula II
(II) in which Y is N, P or As and R1 to R4 independently of one another are C1-18-alkyl, benzyl, phenyl or naphthyl, is used as the con-ductive salt.
(II) in which Y is N, P or As and R1 to R4 independently of one another are C1-18-alkyl, benzyl, phenyl or naphthyl, is used as the con-ductive salt.
6. The process according to claim 5, wherein a compound of the formula II in which Y is N or P, R1 is benzyl or phenyl and R2 to R4 are straight-chain alkyl with in each case 1-12 C atoms or phenyl, or R1 to R4 are straight-chain alkyl with in each case 1-12 C atoms, is used.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH67884 | 1984-02-13 | ||
| CH678/84-6 | 1984-02-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1255686A true CA1255686A (en) | 1989-06-13 |
Family
ID=4192609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000473999A Expired CA1255686A (en) | 1984-02-13 | 1985-02-11 | (2-fluoro-5,6,11,12-tetraselenotetracene).sub.2 chloride, process for its preparation and its use |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4601853A (en) |
| EP (1) | EP0153905B1 (en) |
| JP (1) | JPH0633285B2 (en) |
| CA (1) | CA1255686A (en) |
| DE (1) | DE3562248D1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6292424A (en) * | 1985-10-18 | 1987-04-27 | 松下電器産業株式会社 | Solid electrolytic capacitor |
| CH664963A5 (en) * | 1985-10-18 | 1988-04-15 | Ciba Geigy Ag | DIFLUORED (5,6,11,12-TETRASELENOTETRACEN) 2-HALOGENIDES, METHOD FOR THE PRODUCTION AND USE THEREOF. |
| US5153321A (en) * | 1987-04-03 | 1992-10-06 | Ciba-Geigy Corporation | Antistatic and electrically conducting polymers and moulding materials |
| ES2032222T3 (en) * | 1987-04-03 | 1993-01-16 | Ciba-Geigy Ag | ANTI-STATIC MOLDING POLYMERS AND COMPOUNDS AND ELECTRICITY CONDUCTORS. |
| DE58903321D1 (en) * | 1988-05-27 | 1993-03-04 | Ciba Geigy Ag | SUBSTITUTED BISACYLOXYNAPHTACENES AND METHOD FOR PRODUCING TETRATHIOTETRACENES. |
| EP0344108A3 (en) * | 1988-05-27 | 1991-03-27 | Ciba-Geigy Ag | Electrically active ultrathin films |
| EP0344111A3 (en) * | 1988-05-27 | 1990-04-04 | Ciba-Geigy Ag | Substituted tetrathio- and tetraselenotetracenes |
| DE58907567D1 (en) * | 1988-09-30 | 1994-06-01 | Ciba Geigy | Antistatic and electrically conductive composition. |
| EP0362143B1 (en) * | 1988-09-30 | 1995-11-15 | Ciba-Geigy Ag | Antistatic and electrically conductive relief images, process for manufacturing the same, coating material and radiation-sensitive polymers |
| DE58909496D1 (en) * | 1988-09-30 | 1995-12-21 | Ciba Geigy Ag | Electrically conductive carrier material and polymer films and process for their production. |
| TW242683B (en) * | 1992-02-18 | 1995-03-11 | Ciba Geigy | |
| JP2021042483A (en) * | 2019-09-06 | 2021-03-18 | 王子ホールディングス株式会社 | Book sheet and manufacturing method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3769276A (en) * | 1971-08-05 | 1973-10-30 | American Cyanamid Co | Selenium and tellurim compounds of halogenated arenes and preparation |
| CH591473A5 (en) * | 1974-08-09 | 1977-09-15 | Ciba Geigy Ag | |
| CH612964A5 (en) * | 1975-09-19 | 1979-08-31 | Ciba Geigy Ag | |
| JPS5627139A (en) * | 1979-08-09 | 1981-03-16 | Ibm | Electronnbeam resist composition |
| SU899561A1 (en) * | 1980-04-02 | 1982-01-23 | Отделение ордена Ленина института химической физики АН СССР | Tetraselenotetracene fluoride as organic conductor and process for preparing the same |
| JPS58169769A (en) * | 1982-03-30 | 1983-10-06 | Toshiba Corp | Solid electrolytic cell |
| US4522754A (en) * | 1982-11-12 | 1985-06-11 | Ciba Geigy Corporation | Metallically conducting (2-fluoro-5,6,11,12-tetraselenotetracene)2 -bromide |
-
1985
- 1985-02-04 US US06/697,995 patent/US4601853A/en not_active Expired - Fee Related
- 1985-02-07 DE DE8585810046T patent/DE3562248D1/en not_active Expired
- 1985-02-07 EP EP85810046A patent/EP0153905B1/en not_active Expired
- 1985-02-08 JP JP60022079A patent/JPH0633285B2/en not_active Expired - Lifetime
- 1985-02-11 CA CA000473999A patent/CA1255686A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0633285B2 (en) | 1994-05-02 |
| EP0153905A1 (en) | 1985-09-04 |
| DE3562248D1 (en) | 1988-05-26 |
| US4601853A (en) | 1986-07-22 |
| EP0153905B1 (en) | 1988-04-20 |
| JPS60184088A (en) | 1985-09-19 |
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