9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymers and use thereof

Abstract

The problem addressed was that of providing novel polymers which are preparable with a low level of complexity, with the possibility of controlled influence on the physicochemical properties thereof within wide limits in the course of synthesis, and which are usable as active media in electrical charge storage elements for high storage capacity, long lifetime and stable charging/discharging plateaus. 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymers consisting of an oligomeric or polymeric compound of the general formula I have been found. ##STR00001##

Claims

1. A 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymer, comprising: an oligomeric or polymeric compound having a structure of the formula I ##STR00034## wherein R.sub.1 to R.sub.7 are each independently hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, alkylthio groups, haloalkyl groups, haloalkoxy groups, cycloalkyl groups, cycloalkoxy groups, aryl groups, heteroaryl groups, aryloxy groups, aralkyl groups, carboxylic acid groups, sulphonic acid groups, amino groups, monoalkylamino groups, dialkylamino groups, nitro groups, cyano groups, hydroxyl groups, alkylcarbonyl groups, alkenylcarbonyl groups, alkynylcarbonyl groups, carboxylic ester groups, carboxamide groups, sulphonic ester groups, thiol groups, halogen atoms or a combination of these groups or atoms, R.sub.8 to R.sub.11 are each independently hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, alkylthio groups, haloalkyl groups, haloalkoxy groups, cycloalkyl groups, cycloalkoxy groups, aryl groups, heteroaryl groups, aryloxy groups, aralkyl groups, amino groups, monoalkylamino groups, dialkylamino groups, nitro groups, cyano groups, hydroxyl groups, alkylcarbonyl groups, alkenylcarbonyl groups, alkynylcarbonyl groups, carboxylic ester groups, carboxamide groups, sulphonic ester groups, thiol groups, halogen atoms or a combination of these groups or atoms, the R.sub.8 and R.sub.9 substituents, the R.sub.10 and R.sub.11 substituents, or both the R.sub.8 and R.sub.9 substituents and the R.sub.10 and R.sub.11 substituents form an aromatic, heteroaromatic or nonaromatic ring comprising five to seven atoms, X is an organic group obtained by a polymerization reaction of at least one functionality selected from the group consisting of an organic double bond, an organic triple bond, an oxirane and an aziridine, and n is an integer greater than or equal to 2.

2. The 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymer according to claim 1, wherein X is an organic group having a structure of one of the formulas II-XIV: ##STR00035## ##STR00036## wherein R.sub.12 to R.sub.28 are each independently hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, alkylthio groups, haloalkyl groups, haloalkoxy groups, cycloalkyl groups, cycloalkoxy groups, aryl groups, heteroaryl groups, aryloxy groups, aralkyl groups, carboxylic acid groups, sulphonic acid groups, amino groups, monoalkylamino groups, dialkylamino groups, nitro groups, cyano groups, hydroxyl groups, alkylcarbonyl groups, alkenylcarbonyl groups, alkynylcarbonyl groups, carboxylic ester groups, carboxamide groups, sulphonic ester groups, thiol groups, halogen atoms or a combination of these groups or atoms, R.sub.30 to R.sub.32 are each independently hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, alkylthio groups, haloalkyl groups, haloalkoxy groups, cycloalkyl groups, cycloalkoxy groups, aryl groups, heteroaryl groups, aryloxy groups, aralkyl groups, carboxylic acid groups, sulphonic acid groups, amino groups, monoalkylamino groups, dialkylamino groups, nitro groups, cyano groups, hydroxyl groups, alkylcarbonyl groups, alkenylcarbonyl groups, alkynylcarbonyl groups, carboxylic ester groups, carboxamide groups, sulphonic ester groups, thiol groups, halogen atoms or a combination of these groups or atoms, R.sub.34 to R.sub.36 are each independently hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, alkylthio groups, haloalkyl groups, haloalkoxy groups, cycloalkyl groups, cycloalkoxy groups, aryl groups, heteroaryl groups, aryloxy groups, aralkyl groups, carboxylic acid groups, sulphonic acid groups, amino groups, monoalkylamino groups, dialkylamino groups, nitro groups, cyano groups, alkylcarbonyl groups, alkenylcarbonyl groups, alkynylcarbonyl groups, carboxylic ester groups, carboxamide groups, sulphonic ester groups, halogen atoms or a combination of these groups or atoms, R.sub.37 to R.sub.39 are each independently hydrogen atoms, alkyl groups, alkenyl groups, alkoxy groups, alkylthio groups, haloalkyl groups, haloalkoxy groups, cycloalkyl groups, cycloalkoxy groups, aryl groups, heteroaryl groups, aryloxy groups, aralkyl groups, carboxylic acid groups, sulphonic acid groups, amino groups, monoalkylamino groups, dialkylamino groups, nitro groups, cyano groups, hydroxyl groups, alkylcarbonyl groups, alkenylcarbonyl groups, alkynylcarbonyl groups, carboxylic ester groups, carboxamide groups, sulphonic ester groups, thiol groups, halogen atoms or a combination of these groups or atoms, A is an oxygen atom, a sulphur atom or an N(R.sub.33) group, wherein R.sub.33 is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, a haloalkyl group, a haloalkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, a heteroaryl group, an aryloxy group, an aralkyl group, a carboxylic acid group, a sulphonic acid group, a nitro group, an alkylcarbonyl group, an alkenylcarbonyl group, an alkynylcarbonyl group, a carboxylic ester group, a carboxamide group, or a sulphonic ester group, A.sub.1 and A.sub.2 are each independently a covalent bond, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, a haloalkyl group, a haloalkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, a heteroaryl group, an aryloxy group, an aralkyl group, a monoalkylamino group, a dialkylamino group, an alkylcarbonyl group, an alkenylcarbonyl group, an alkynylcarbonyl group, a carboxylic ester group, a carboxamide group, or a sulphonic ester group, A.sub.3 and A.sub.4 are each independently a covalent bond, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkoxy group, an aryl group, a heteroaryl group, an aryloxy group, an aralkyl group, a dialkylamino group, an alkylcarbonyl group, an alkenylcarbonyl group, an alkynylcarbonyl group, a carboxylic ester group, a carboxamide group, or a sulphonic ester group, A.sub.5 and A.sub.6 are each independently a covalent bond, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, a haloalkyl group, a haloalkoxy group, a cycloalkyl group, a cycloalkoxy group, an aryl group, a heteroaryl group, an aryloxy group, an aralkyl group, a monoalkylamino group, a dialkylamino group, an alkylcarbonyl group, an alkenylcarbonyl group, an alkynylcarbonyl group, a carboxylic ester group, a carboxamide group, or a sulphonic ester group, Ar is an independently substituted cycloalkyl group, cycloalkoxy group, aryl group, heteroaryl group, aryloxy group, or aralkyl group.

3. An electrical charge storage device, comprising: an active electrode material, the active electrode material comprising the 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymer according to claim 1.

4. The electrical charge storage device according to claim 3, wherein the active electrode material comprising the 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymer is present as a full or partial surface coating of electrode elements of the electrical charge storage device.

5. An electrode slurry, comprising: the 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymer according to claim 1.

6. The 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymer according to claim 1, wherein at least five of the R.sub.1 to R.sub.7 substituents are hydrogen atoms and zero to two R.sub.1 to R.sub.7 substituents are non-hydrogen atoms.

7. The 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymer according to claim 6, wherein the non-hydrogen atoms if present are each independently halogen atoms, alkyl groups, alkoxy groups, cyano groups, or nitro groups.

8. The 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymer according to claim 1, wherein the R.sub.8 and R.sub.9 substituents, the R.sub.10 and R.sub.11 substituents, or both the R.sub.8 and R.sub.9 substituents and the R.sub.10 and R.sub.11 substituents form a nonaromatic ring comprising at least one functionality selected from the group consisting of alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, alkylthio groups, haloalkyl groups, haloalkoxy groups, cycloalkyl groups, cycloalkoxy groups, aryl groups, heteroaryl groups, aryloxy groups, aralkyl groups, amino groups, monoalkylamino groups, dialkylamino groups, alkylcarbonyl groups, alkenylcarbonyl groups, alkynylcarbonyl groups, carboxylic ester groups, carboxamide groups, and sulphonic ester groups.

9. The 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymer according to claim 1, wherein at least one of the R.sub.8 to R.sub.11 substituents is an alkyl group, an alkythio group, or a thiol group.

10. The 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymer according to claim 1, wherein at least one of the R.sub.8 to R.sub.11 substituents is a methyl group, an ethyl group, methylthio group, or an ethylthio group.

11. The 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymer according to claim 2, wherein the R.sub.18 substituent if present, the R.sub.25 substituent if present, or both are a hydrogen atom.

12. The 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymer according to claim 2, wherein at least one of the following parameters is met; at least two of the R.sub.12 to R.sub.14 substituents if present are hydrogen atoms and zero to one of the R.sub.12 to R.sub.14 substituents if present are non-hydrogen atoms, at least two of the R.sub.15 to R.sub.17 substituents if present are hydrogen atoms and zero to one of the R.sub.15 to R.sub.17 substituents if present are non-hydrogen atoms, at least two of the R.sub.19 to R.sub.21 substituents if present are hydrogen atoms and zero to one of the R.sub.19 to R.sub.21 substituents if present are non-hydrogen atoms, at least two of the R.sub.22 to R.sub.24 substituents if present are hydrogen atoms and zero to one of the R.sub.22 to R.sub.24 substituents if present are non-hydrogen atoms, or at least two of the R.sub.26 to R.sub.28 substituents if present are hydrogen atoms and zero to one of the R.sub.26 to R.sub.28 substituents if present are non-hydrogen atoms.

13. The 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymer according to claim 12, wherein the non-hydrogen atoms if present are each independently halogen atoms, alkyl groups, alkoxy groups, cyano groups, or nitro groups.

14. The 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymer according to claim 2, wherein at least one of the following parameters is met; at least two of the R.sub.30 to R.sub.32 substituents if present are hydrogen atoms and zero to one of the R.sub.30 to R.sub.32 substituents if present are non-hydrogen atoms, at least two of the R.sub.34 to R.sub.36 substituents if present are hydrogen atoms and zero to one of the R.sub.34 to R.sub.36 substituents if present are non-hydrogen atoms, or at least two of the R.sub.37 to R.sub.39 substituents if present are hydrogen atoms and zero to one of the R.sub.37 to R.sub.39 substituents if present are non-hydrogen atoms.

15. The 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymer according to claim 14, wherein the non-hydrogen atoms if present are each independently halogen atoms, alkyl groups, alkoxy groups, cyano groups, or nitro groups.

16. The 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymer according to claim 2, wherein A if present is an oxygen atom.

17. The 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymer according to claim 2, wherein the A.sub.1 substituent if present, the A.sub.2 substituent if present, the A.sub.3 substituent if present, the A.sub.4 substituent if present, the A.sub.5 substituent if present, and the A.sub.6 substituent if present are each independently a covalent bond or an alkyl group.

18. The electrical charge device according to claim 3, wherein the electrical charge storage device is a secondary battery.

19. The electrical charge device according to claim 4, wherein the electrical charge storage device is a secondary battery.

20. A method of forming an electrode, the method comprising: providing an electrode slurry comprising the 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymer according to claim 1; wherein the electrode comprises an active electrode material, the active electrode material comprising the 9,10-Bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene polymer, and wherein the active electrode material is present as a full or partial surface coating of the electrode.

Description

(1) The invention is to be illustrated in detail hereinafter by the working examples for preparation and use shown in the drawings.

(2) The drawings show:

(3) FIG. 1: Cyclic voltammogram (14 cycles) of an electrode produced according to Example 4.

(4) FIG. 2 Charge/discharge curves of the first and two hundred and fiftieth charging/discharging cycle of a secondary battery produced according to Example 5.

(5) FIG. 3: Charging/discharging behaviour of these condary battery produced according to Example 5.

(6) FIG. 4: Cyclic voltammogramm (20 cycles) of an electrode produced according to Example 9.

(7) FIG. 5: Charging/discharging behaviour of these condary battery produced according to Example 10.

(8) FIG. 6 Charging/discharging behaviour of these condary zinc-organic battery at different charge rates (10 C=full charging in 6 minutes; 20 C=full charging in 3 minutes; 40 C=full charging in 1 minute, 30 seconds; 60 C=full charging in 1 minute; 90 C=full charging in 45 seconds; 120 C=full charging in 30 seconds) produced according to Example 10.

(9) .sup.1H and .sup.13C NMR spectra were recorded with a Bruker AC 300 (300 MHz) spectrometer at 298 K. Elemental analyses were conducted with a Vario ELIII-Elementar Euro instrument and an EA-HekaTech instrument. For cyclic voltammetry and galvanostatic experiments, a Biologic VMP 3 potentiostat was available. Size exclusion chromatography was conducted on an Agilent 1200 series system (degasser: PSS, pump: G1310A, autosampler: G1329A, oven: Techlab, DAD detector: G1315D, RI detector: G1362A, eluent: DMAc+0.21% LiCl, 1 ml/min, temperature: 40 C., column: PSS GRAM guard/1000/30 ).

(10) ##STR00031## ##STR00032##

EXAMPLE 1

Synthesis of 2-vinylanthraquinone (2 in the above Scheme 17)

(11) 2-Iodoanthraquinone (1.74 g, 5.22 mmol), bis(dibenzylideneacetone)palladium(0) (0.060 g, 0.104 mmol) and biphenyl-2-yidi-tert-butylphosphine (0.062 g, 0.209 mmol) are dissolved in a 0.3 M solution of tetrabutylammonium fluoride in tetrahydrofuran. The solution is purged with argon, and 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane (0.902 ml, 2.61 mmol) is added dropwise. The mixture is stirred at 80 C. under an argon atmosphere for eight hours. The reaction mixture is cooled to room temperature and added to 250 ml of ethanol. The precipitate is filtered off and washed twice with n-hexane. After drying under reduced pressure, almost pure 2-vinylanthraquinone (2) (1.175 g, 5.02 mmol, 96%) is obtained as a yellowish solid, the purity of which is sufficient for the next reaction step.

(12) Anal. Calcd for C.sub.16H.sub.10O.sub.2: C, 81.90; H, 4.30. Found: C, 81.85; H, 4.31. .sup.1H NMR, (CDCl.sub.3, 300 MHz, ppm): 5.54 (d, 1H), 6.05 (d, 1H), 6.87 (dd, 1H), 7.80 (m, 3H), 8.32 (m, 4H). .sup.13C NMR (CDCl.sub.3, 75 MHz, ppm): 183.2, 182.6, 143.2, 135.4, 134.1, 134.0, 133.8, 133.6, 133.5, 132.5, 131.4, 128.3, 127.8, 127.2, 124.8, 118.4.

EXAMPLE 2

Synthesis of 2,2-(2-vinylanthracene-9,10-diylidene)bis(1,3-dithiol) (3 in Scheme 17)

(13) Dimethyl-1,3-dithiol-2-yl phosphonate (733 mg, 3.45 mmol) is dissolved in 10 ml of tetrahydrofuran under an argon atmosphere, and the reaction mixture is cooled down to 78 C. A 2.5 M solution of n-butyllithiutn in n-hexane (1.5 ml 3.75 mmol) is added dropwise to the reaction mixture within five minutes. The reaction mixture is stirred at 78 C. for two hours. Thereafter, a solution of 2-vinylanthraquinone (352 mg, 1.50 mmol) in 11.5 ml of tetrahydrofuran is added dropwise at 78 C. After one hour at 78 C., the reaction mixture is stirred at room temperature for a further four hours. 50 ml of ethyl acetate are added to the reaction mixture, and the mixture is extracted twice with water (35 ml) and once with brine (20 ml). The organic phase is dried over magnesium sulphate, filtered and concentrated under reduced pressure. The resultant crude product is purified by means of column chromatography (silica gel; n-hexane/toluene, 1/1). This gives 700 mg (2.12 mmol, 51%) (3) as a yellow powder. Anal. calcd for C2214.10N4: C, 64.99; H, 3.47, S, 31.54. Found: C, 64.81; H, 3.58, S, 30.95. 1H NMR (CD2Cl2, 300 MHz, ppm): 7.78 (d, 1H), 7.74-7.69 (m, 2H), 7.67 (s, 1H), 7.38 (d, 1H), 7.36 (m, 2H), 6.81 (dd, 1H), 6.39 (s, 2H), 6.38 (s, 1H), 5.84 (d, 1H), 5.33 (d, 1H). ESI-MS, m/z 406.00 [M+].

EXAMPLE 3

Synthesis of poly(2,2-(2-vinylanthracene-9,10-diylidene)bis(1,3-dithiol)) (4 in Scheme 17)

(14) 50 mg of 2,2-(2-vinylanthracene-9,10-diylidene)bis(1,3-dithiol) (3) are dissolved in 0.25 ml of dimethyl sulphoxide, and 1.01 mg of AIBN (0.0062 mmol, 5 mol %) are added. The reaction mixture is degassed with argon for five minutes and stirred at 80 C. for 18 hours. Thereafter, the reaction solution is added to 50 ml of dichloromethane, in order to precipitate the product. This forms 30 mg of poly(2,2-(2-vinylanthracene-9,10-diylidene)bis(1,3-dithiol) (4) as an orange solid.

(15) Anal. Calcd for C.sub.22H.sub.10N.sub.4: C, 80.00; H, 3.10, N, 16.90. Found: C, 79.96; H, 3.13, N, 16.95. .sup.1H NMR (DMF-d.sub.7, 300 MHz, ppm): 8.83 to 7.48 (br, 7H), 2.62 to 1.31 (br, 3H). SEC: M.sub.n 6.0210.sup.3 g/mol (PS standard), PDI: 1.66.

EXAMPLE 4

Production of an Electrode with poly(2,2-(2-vinylanthracene-9,10-diylidene)bis(1,3-dithiol)) (4 in Scheme 17), cf. FIG. 1

(16) A solution consisting of poly(2,2-(2-vinylanthracene-9,10-diylidene)bis(1,3-dithiol)) (4) in NMP (N-methyl-2-pyrrolidone) (10 mg/ml) was added to carbon fibres (VGCF; Showa-Denko) as conductivity additive and poly(vinylidene fluoride) (PVDF; Sigma Aldrich) as binder additive (ratio: 10/80/10 v/m/m), These materials were mixed in a mortar for ten minutes, and the resulting paste was applied to an aluminium foil using a coating blade method (thickness: 0.015 mm, MTI Corporation). The electrode is dried at 100 C. for 24 hours.

(17) The electrode is dipped into an electrolyte solution (0.1 M LiClO.sub.4 in 1,2-di-methoxy-ethane/propylene carbonate 4/1). For the cyclic voltammetry measurement, a half-cell consisting of said electrode as working electrode and an Ag/AgNO.sub.3 electrode as reference electrode, and also a platinum mesh as counterelectrode, is constructed (FIG. 1).

(18) The cyclic voltammogram shows a stable redox reaction at 0.12 V.

EXAMPLE 5

Production of an Li Polymer Battery

(19) The electrode described in Example 4 is introduced into a secondary battery (Li polymer battery) under an argon atmosphere. The electrolyte used is a 0.1 M solution of LiClO.sub.4 in 1,2-di-methoxy-ethane/propylene carbonate 4/1; the counterelectrode used is a piece of elemental lithium. The two electrodes are separated from one another by these parator (a porous polypropylene membrane, Celgard). The battery shows a charge plateau at 3.4 V and a discharge plateau at 3.2 V (FIG. 2).

(20) In the first charge/discharge cycle, the battery shows a capacity of 108 mAh/g (82% of the the oretically possible capacity); after 500 charge/discharge cycles, the battery shows a capacity of 82 mAh/g (FIG. 3) at an average coulomb efficiency of 99%.

(21) Scheme 18 shows the schematic representation of the synthesis of poly(2,2-(2-ethynylanthracene-9,10-diylidene)bis(1,3-dithiol)):

(22) ##STR00033##

EXAMPLE 6

Synthesis of 2-ethynylanthraquinone (7 in Scheme 18)

(23) 2-Bromoanthraquinone (5 in Scheme 18; 1.00 g, 3.5 mmol), copper(I) iodide (0.012 mg, 0.007 mmol) and bis(triphenylphosphine)palladium(II) dichloride (0.042 g, 0.035 mmol) are dissolved in a 1/1 v/v mixture of tetrahydrofuran and triethylamine (11 ml). The solution is purged with argon, and trimethylsilylacetylene (0.54 ml, 3.8 mmol) is added dropwise. The mixture is stirred at 80 C. for six hours under an argon atmosphere. The reaction mixture is cooled to room temperature and 50 ml of chloroform are added. The solution is washed once with 50 ml of saturated aqueous ammonium chloride solution, once with 50 ml of water and once with 50 ml of saturated aqueous sodium chloride solution, dried over magnesium sulphate, filtered and concentrated to dryness under reduced pressure. The crude product is purified by column chromatography (chloroform/n-hexane 5/1), The 2-((trimethylsilypethynyl)anthraquinone obtained (800 mg, 2.64 mmol) is dissolved in 25 ml of an acetone/methanol solution in a ratio of 2/1. Added to this solution is sodium hydroxide (105.2 mg, 2.64 mmol). The reaction mixture is stirred at room temperature for three hours, diluted with 50 ml of chloroform and washed once with 50 ml of saturated aqueous ammonium chloride solution, once with 50 ml of water and once with 50 ml of saturated aqueous sodium chloride solution, dried over magnesium sulphate, filtered and concentrated to dryness under reduced pressure the crude product is purified by column chromatography (chloroform/n-hexane 5/1), This gave 682 mg of 2-ethynylanthraquinone (7 in Scheme 18) as brown crystals.

(24) Anal. calcd for C.sub.16H.sub.8O.sub.2: C, 82.8; H, 3.5%. Found: C, 82.7; H, 3.3%. .sup.1H NMR (CDCl.sub.3, 300 MHz, ppm, TMS): d 8.32 (Ph, 4H), 7.83 (Ph, 3H), 3.37 (CH, 1H). .sup.13C NMR (CDCl.sub.3, 300 MHz, ppm, TMS): d 182.8, 137.5, 134.8, 134.7, 133.9, 133.8, 133.3, 131.3, 128.7, 127.8, 127.5, 82.4, 82.3. MS (m/z) calcd for M.sup.+ 232.1. Found: 233.1.

EXAMPLE 7

Synthesis of 2,2-(2-Ethynylanthracene-9,10-diylidene)bis(1,3-dithiol) (8 in Scheme 18)

(25) Dimethyl 1,3-dithiol-2-ylphosphonate (823 mg, 3.2 mmol) is dissolved in 5 ml of tetrahydrofuran under an argon atmosphere and the reaction mixture is cooled to 78 C. A 2.5 M solution of n-butyllithium in n-hexane (1.5 ml, 3.75 mmol) is added dropwise to the reaction mixture over the course of five minutes. The reaction mixture is stirred at 78 C. for two hours. Thereafter a solution of 2-ethynylanthraquinone (7 in Scheme 18; 352 mg, 1.50 mmol) in 11.5 ml of tetrahydrofuran is added dropwise at 78 C., After an hour at 78 C., the reaction mixture is stirred at room temperature for four hours more. The reaction mixture is admixed with 50 ml of chloroform, and the mixture is extracted twice with water (35 ml) and once with saturated aqueous sodium chloride solution (20 ml). The organic phase is dried over magnesium sulphate, filtered and concentrated under reduced pressure. The crude product obtained is purified by column chromatography (silica gel n-hexaneltoluene, 1/1), This gives 418 mg (1.03 mmol, 69%) of product (8 in Scheme 18) as a yellow solid. Anal. Calcd for C22H.sub.12S.sub.4: C, 65.31; H, 2.99, S, 31.70. Found: C, 65.20; H, 2.90, S, 31.62.

EXAMPLE 8

Synthesis of poly(2,2(2-ethynylanthracene-9,10-diylidene)bis(1,3-dithiol) (9 in Scheme 18)

(26) Under argon, a solution of 50 mg of 2,2-(2-ethynylanthracene-9,10-diylidene)bis(1,3-dithiol) (8 in Scheme 18) in 0.25 ml of N,N-dimethylformamide is admixed with a solution of 1.49 mg of bicyclo[2.2.1]hepta-2,5-diene-rhalium(I) chloride dimer in 0.1 ml of N,N-dimethylformamide. The reaction solution is stirred at room temperature for 18 hours. Thereafter the reaction solution is added to 50 ml of acetonitrile in order to precipitate the product. This procedure gives rise to 40 mg of poly-2,2-(2-ethynylanthracene-9,10-diylidene)bis(1,3-dithiol) (9 in Scheme 18) as an orange solid.

(27) Anal. Calcd for C.sub.22H.sub.12S.sub.4: C, 65.31; H, 2.99, S, 31.70. Found: C, 65.29; H, 2.80, S, 31.52. SEC: M.sub.n 8.9210.sup.3 g/mol (PS standard), PDI: 1.84.

EXAMPLE 9

Production of an Electrode with poly(2,2-(2-ethynylanthracene-9,10-diylidene)bis dithiol))

(28) A solution consisting of poly(2,2(2-ethynylanthracene-9,10-diyhdene)bis(1,3-dithiol)) (9 in Scheme 18) in NMP (N-methyl-2-pyrrolidone) (5 mg/nil) was added to carbon fibres (MWCNT, Sigma-Aldrich) as conductivity additive (ratio: polymer/conductivity additive 50/50 m/m). These materials were mixed in a mortar for ten minutes, and the resulting paste was applied to a graphite foil using a coating blade method (thickness: 0.254 mm, Alfa Aesar), The electrode is dried at 100 C. for 24 hours.

(29) The electrode is dipped into an electrolyte solution (2 M Zn(BF.sub.4).sub.2 in water). For the cyclic voltammetry measurement, a half-cell consisting of said electrode as working electrode and an Ag/AgCl electrode as reference electrode, and also a zinc foil as counterelectrode, is constructed.

(30) The cyclic voltammogram (FIG. 4) shows a stable redox reaction between 0.8 and 1.6 V.

EXAMPLE 10

Production of a Zinc Polymer Battery

(31) The electrode described in Example 9 is introduced into a secondary battery (Zn polymer battery). In this battery, zinc metal functions as the anode and the polymer composite electrode as cathode. The electrolyte used is a 2 M solution of Zn(BF.sub.4).sub.2 in water; the counterelectrode used is a piece of elemental zinc foil. The two electrodes are separated from one another by the electrolytes (distance about 3 mm). The battery shows a charge plateau at 1.2 V and a discharge plateau at 1.1 V (FIG. 5).

(32) In the first charge/discharge cycle, at a rate of 10 C (=full charging in 6 minutes), the battery shows a capacity of 100 mAh/g (78% of the the oretically possible capacity); after 100 charge/discharge cycles, the battery shows a capacity of 95 mAh/g (FIG. 6) at an average coulomb efficiency of 99% (coulomb efficiency=ratio of the charge withdrawn from the battery during a charge/discharge cycle to the charge supplied to the battery during the same charge/discharge cycle). The battery can be charged at up to 120 C. At a charging rate of 120 C. (full charging in 30 seconds), the battery shows a capacity of 55 mAh/g (40% activity of material).