AU3223093A - Novel salts of fullerenes - Google Patents
Novel salts of fullerenesInfo
- Publication number
- AU3223093A AU3223093A AU32230/93A AU3223093A AU3223093A AU 3223093 A AU3223093 A AU 3223093A AU 32230/93 A AU32230/93 A AU 32230/93A AU 3223093 A AU3223093 A AU 3223093A AU 3223093 A AU3223093 A AU 3223093A
- Authority
- AU
- Australia
- Prior art keywords
- fullerene
- group
- anion
- composition
- potential
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229910003472 fullerene Inorganic materials 0.000 title claims description 65
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims description 46
- 150000003839 salts Chemical class 0.000 title claims description 37
- -1 fullerene anion Chemical class 0.000 claims description 36
- 150000001768 cations Chemical class 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 150000001450 anions Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 25
- 239000002904 solvent Substances 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000804 electron spin resonance spectroscopy Methods 0.000 description 5
- 230000005291 magnetic effect Effects 0.000 description 5
- 238000001736 differential pulse polarography Methods 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011877 solvent mixture Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000005292 diamagnetic effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000003115 supporting electrolyte Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 230000005343 Curie-Weiss law Effects 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 241000220324 Pyrus Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- YLFIGGHWWPSIEG-UHFFFAOYSA-N aminoxyl Chemical compound [O]N YLFIGGHWWPSIEG-UHFFFAOYSA-N 0.000 description 1
- 238000006758 bulk electrolysis reaction Methods 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000426 electronic spectroscopy Methods 0.000 description 1
- 238000002265 electronic spectrum Methods 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 235000021017 pears Nutrition 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-O phenylphosphanium Chemical compound [PH3+]C1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-O 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/152—Fullerenes
- C01B32/156—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/14—Alkali metal compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
NOVEL SALTS OF FULLERENES
FIELD OF THE INVENTION
The present invention relates to novel salts of fullerenes, also known as fulleride salts, their preparation and use.
BACKGROUND OF THE INVENTION
Diamond and graphite are two well known allotropic forms of carbon. Another form, the fullerenes, have been prepared by graphite volatilization (See W. Kratschmer et al , Nature, 347, p. 354 (1990)). Potassium and other metal complexes of fullerenes have been observed in the gas phase by mass spectrometry (See D. M. Cox et al , J. Chem. Phvs. 88(3), 1588 (1988)).
Fullerenes are hollow molecules composed only of carbon atoms and constitute a new allotropic form of carbon. Typically, fullerenes each have carbon atoms arranged as 12 pentagons, but differing numbers of hexagons having the formula C2n where n is equal to or greater than 16 (hereinafter "fullerenes"). The pentagons are required in order to allow the curvature and eventual closure of the closed surface upon itself. The most abundant species of fullerenes identified to date is the C60 molecule or Buck insterfullerene (here¬ inafter "C6θ"). C60 consists of 12 pentagons and 20 hexagons. However, other species, including C70 have also been identified.
SUMMARY OF THE INVENTION
The portion of this invention that relates to Cβo fulleride salts was first disclosed by applicants at a seminar in Boston, Massachusetts on November 29, 1990, and subsequently published in Mat. Res. Soc. Svmp. Proc. Vol. 206, p. 659 (1991). This invention provides new compositions of matter having the formula AnCx, wherein Cx is a fullerene anion wherein x is preferably selected from the group consisting of C60 and C70 and wherein A is a monovalent cation.
Preferred monovalent cations, in accordance with the present inven¬ tion, include ammonium cations, alkyl ammonium cations such as quater¬ nary ammonium cations, alkali metal cations, phosphonium and arsoniu cations, especially organophosphonium and organoarsonium ions, partic¬ ularly phenylphosphonium and phenylarsonium cations. The preferred fullerene used in the practice of the present invention is C60-
In one embodiment of the present invention, the fulleride salt compounds of the present invention are prepared by passing an electric current through (electrolyzing) a non-aqueous solution of fullerenes in the presence of a soluble salt containing a cation, A, of the AnCχ compound to be formed. The electric potential is applied for a time sufficient to generate fullerene anions in the solution. In another embodiment of the present invention, the fulleride salt compounds are prepared in the solid state. The compounds of the present invention exhibit reversible electrochemical reduction; and, consequently, are particularly useful as electrode components in electrochemical cells such as secondary batteries.
The fullerene anions, Ceo'-^ and C70~y, wherein y is a charge of from 1 to 3, specifically 1, 2, and 3 in the compound of the present invention contain unpaired electrons and thus have paramag¬ netic properties. In the case of, for example, C6o~l and Cδo----, these properties are confirmed by electron spin resonance spectroscopy ("ESR") for the tetralkyl ammonium fulleride salt containing the C60~* monoanion. The magnitude of the magnetic susceptibility of the compound of the present invention varies with the temperature accord¬ ing to the Curie-Weiss law, which is known to one having ordinary skill in the art. Since a one-to-one magnetic susceptibility tempera¬ ture correspondence exists, these compounds may be used as magnetic thermometers.
Similarly, fulleride salts containing C60"1 monoanions may be used as semiconductors (See P. M. Allemand et al., J. Am. Chem. Soc., 113,2780 (1991)) while those containing C60"3 and alkali-metals may be used as superconductors (See A. F. Hebard et al., Nature 350,600 (1991)).
Alkali salts of C60 also can serve as starting materials for the preparation of other materials. The reaction of the lithium salt of Ceo, for example, with alkyl halides yield alkyl derivatives of fullerenes (See J. W. Bausch et al., J. Am. Che . Soc 113,3205 (1991)) that may be useful as polymer blends, composites and building blocks.
Further, the AnCx fulleride salts are stable in the absence of air and other reactive molecules. Their free radical character may make them suitable as spin labels. Spin labels are usually organic molecules that contain an unpaired electron (for example, a nitroxyl radical) and are used to render diamagnetic molecules to which they are attached susceptible to analysis by magnetic spin resonance techniques. The AnCx spin labels mixed, for example with polymers, may allow valuable information concerning polymer dynamics and struc¬ tures to be obtained.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention encompasses novel compositions of matter having the formula AnCx, wherein Cx is a fullerene anion, wherein Cx is preferably selected from the group consisting of Cδo and C70, wherein A is a monovalent cation and wherein n is an integer from 1 to 3 inclusive, specifically 1, 2, and 3. The cation, A, may be selected from a wide range of cations. The fullerene anion is further selected from the group consisting of monovalent, divalent and tri- valent anions. Its valence, however, depends on the formula of the monovalent cation, An. Thus, for example where the monovalent cation, An, has the formula (A+1)ι, Cx will be a monovalent anion; where An has the formula (A+l)2, Cx will be a divalent anion; for (A+l)3, Cx will be a trivalent anion. Particularly preferred cations for A include ammonium and alkyl ammonium cations, organophosphoniu or organoarsonium cations, especially tetraorganophosphoniu and tetra- organoarsonium ions, such as tetraphenylphosphonium and tetraphenyl- arsonium cations, alkali metal cations, and the like. Among the alkali metal cations, Li, Na and K are especially preferred. The
preferred fullerene used in the practice of the present invention is C60-
The starting materials for the practice of the present invention can be obtained from commercial sources. In addition, the fullerenes may be prepared by graphite volatilization (see W. Kratschmer, et al, Nature. 347, p. 354 (1990)).
When the compounds of the present invention are made by electrolyzing a non-aqueous solution containing fullerenes and a soluble salt of a cation, A, such as one of the aforementioned cat¬ ions, the electrochemical reduction of fullerenes is conducted prefer¬ ably in a low or high polarity solvent as required to dissolve the reactants, but which will be inert to the reaction. "Non-aqueous" as used herein means solvent systems wherein water, if present, is electrochemically and chemically inert. Thus, by way of example, toluene, dichloromethane in the case where the cation, A, is organic and a high polarity solvent such as dimethyl sulfoxide when the cation A is inorganic. Single, binary or multicomponent mixtures of tetrahy- drofuran, ethylene chloride, toluene, xylenes, dimethyl sulfoxide, dichloromethane, benzene are particularly suitable for dissolving the fullerenes. Additionally, the salt containing the cation, A, of desired compound, AnCx, must have some solubility in the organic solvent system used. Typically, therefore, salts containing organo groups such as, but not restricted to, R4NCI, R4ASU, R4PCI, R4NPF6, and R4NBF4 are particularly suitable. In the foregoing salts, R is selected from the group consisting of hydrogen and an organic moiety. The organic moiety should be chosen in order to render the salt soluble in the solvent system. It is within the skill of one of ordinary skill in the art to make a selection of the appropriate solvent system. R may, for example, be selected from alkyl groups having from 1 to 16 carbon atoms and phenyl groups. Other useful salts include alkali metal salts having anions containing sufficient organic moieties to render the salt soluble in the solvent system. Representative examples include NaBPh4, KBPh4 where ("Ph" as used herein means phenyl or substituted phenyl group). When inorganic salts containing the cation A are used, the solvent system is more
polar. Inorganic salts such as NaBF4, KC1 and KBr should be used with mixtures of tetrahydrofuran, dimethyl sulfoxide, dimethyl formamide, toluene and the like. The relative ratio of components of the solvent mixtures should be such as to insure some degree of solubility of both starting materials; i.e., fullerenes (which are soluble in relatively non-polar solvents) and inorganic salts (more soluble in polar sol¬ vents like dimethyl sulfoxide). It is within the skill of a person with average skill in the art to select the optimum mixture of sol¬ vents suitable for a given inorganic salt containing a desired A cation. The resultant AnCx fulleride salts need not be soluble in the solvent mixtures used and it is preferred that they are not if isola¬ tion of the solid salt is desirable.
A commercially available PAR (Princeton Applied Research) System equipped with Pt wire auxiliary electrode, standard calomel reference electrode (SCE) and a Pt gauze working electrode may be used to reduce, for example, up to gram quantities of the particular fullerene. Other commercial units may be used to prepare larger quantities of fulleride salts. A potentiostat regulates the potential necessary to produce the desired reduction state (salt of anion) of the fullerene in the particular solvent system. The molar ratio of salt to fullerene used in the solvent system will be generally greater than 3:1 and, preferably, will be in the range of about 10 to 20. The potential may be applied using any known source of direct current after immersing the working and reference electrodes into the solvent system. The auxiliary electrode may be isolated from the working electrode compartment during application of the electric potential, the mixture may be stirred, but such is not necessary. Typically, the reaction takes place at room temperature and pressure under a blanket of inert gas. Alternatively, an inert gas (for example, N2, Ar) may be bubbled through the solvent mixture. For example, for the produc¬ tion of CβO"1 monoanion from Cδo a potential of -0.45 V versus SCE in the DMSO solvent system using KBr as supporting electrolyte resulted in production of only the fullerene salts containing C60 monoanion. Since the potential necessary to produce the anions of desired valence is solvent dependent its value can be determined via cyclic volta - metry (CV) or differential pulse polarography (DPP). Care must be
6 -
taken in choosing solvent system, electrolyte, temperature, electrode type, etc. to obtain reversible well separated waves in CV at slow scan speeds. These conditions are necessary for selective production of the particular fullerene salt and to ensure that once produced they are not decomposed during the bulk electrolysis. For typical examples of well separated waves in CV and DPP data on Ceo and C70 fullerenes, see S. M. Gorun et. al, Mat. Res. Soc. Svmp. Proc. 206, 659 (1991).
The process of the present invention may be used to selec¬ tively generate the salt of the fullerene anions in solutions of the fullerenes and other hydrocarbons by applying a current to the solu¬ tion, wherein the current is of sufficiently low voltage to selective¬ ly reduce the particular fullerene to the correspondent salt of the fullerene anion without reducing the other hydrocarbons. The fuller¬ ene anions have the formula Cχ-y, wherein Cx is a fullerene, prefera¬ bly a fullerene selected from the group consisting of Cδo and C70 and wherein y is an integer of from 1 to 3, specifically 1, 2 and 3. The range of electric potentials will vary with the solvent system, but can readily be selected by one having ordinary skill in the art. The electric potential is from about zero to about -0.7 V, when the fullerene anion is selected from the group consisting of C6o~l (when the fullerene is Ceo) and C70"1 when the fullerene is C70; it is from about -0.80 V to about -1.1 V when the fullerene anion is selected from the group consisting of Cδθ"2 (when the fullerene is Cδo) and C7o*2 (when the fullerene is C60) and C7o~2 (when the fullerene is C70); and it is from about -1.3 V to about -1.7 V when the fullerene anion is selected from the group consisting of CβO"3 (when the fuller¬ ene is Cβo) and Zη ~ (when the fullerene is C70). For example, 60~l> which is prepared from Cδo at a potential of -0.70 V in 1:2 dichloromethane/toluene mixtures, may be selectively prepared as the salt of the C60~l anion from mixtures of C60 with other hydrocarbons having higher potentials (that is, having a chemical inertness within the range of potentials at which the Cδo"1 anion is produced) by applying the foregoing chemical potentials to the solution. The salt of the fullerene anion may be present in the solution or precipitated therefrom. The actual voltage may vary, depending on the solvent in which the reduction is conducted. However, the potential should be
chosen within the range of the electrochemical potential necessary to generate the particular salt of the fullerene anion and within the range of chemical inertness for the other hydrocarbons. (For techni¬ cal details see, for example, P. T. Kissinger and Wm. H. Heine an, Editors, Laboratory Techniques in Electrochemistry-, Marcel Decker, Inc., N.Y. (1984); and A. Bard and L. Faulkner, Electrochemical Methods. Wiley and Sons, N.Y. (1980)).
During the electrolysis, the progress of the reaction is monitored by measuring the amount of current that passes through the solution. Alternatively, since the fullerene anions are paramagnetic while the starting fullerenes are diamagnetic, quantitative ESR spectroscopy can be used for the same purpose. Similar results are expected for C70"-1 monoanion. (See, for example M. A. Greaney et al . , J. Phvs. Chem. 95,7142 (1991) for the ESR signatures of the C60'1 and C70"1 and D. Dubois et al., J. Am. Chem. Soc. 113,4364 (1991) for C60"-*-)- For Ceo, applicants found that the most convenient method to detect Ceo"* is the monitoring of the near infrared spectrum of the solution. A strong absorption band centered at approximately 1065 nm is present in Ceo"*-*, but missing in CδO- This band, which is attrib¬ uted to the H0M0-LUM0 (highest occupied molecular orbital-lowest unoccupied molecular orbital) electronic transition of C50"1 disap¬ pears upon oxidation of CδO"1 to δO and can be regenerated upon further reduction. Its position and intensity is practically indepen¬ dent of the A cation, being observed for both organic (e.g., BU4N) and inorganic (e.g., K) salts of C60" » in a variety of solvents. As used herein, "Bu" means "butyl".
The AnC product may be isolated by precipitation; for example, using a non-solvent or precipitating agent, such as toluene or ether or by reducing the volume of the solvent used via vacuum distillation or low temperature freezing. Using this technique, only the fullerene salt precipitates. For example, if KC1 is used as a source of potassium cation, only KCβn, not KC1 is precipitated. Only traces of chloride ions are detectable in the KC60 solid precipitate via scanning electron microscopy energy dispersive spectra technique.
The following examples are intended to demonstrate the invention and not l imit it in any way.
EXAMPLES
In all of the following examples, the solvents were dried and degassed according to standard methods. A blanket of inert gas prevented the contact of the reaction mixture with the atmosphere. All reactions are carried out at ambient temperature and pressure unless stated otherwise. Mixtures of C60/C70 were obtained by solvent extracting the soot produced via the carbon arc synthesis method, as stated in D. M. Cox et al., J. Am. Chem. Soc. 113, 2940 (1991). Pure C60 was produced by chromatography from mixtures of Cδo and C70 fullerenes, as described in the literature. See, for example, D. M. Cox et al., J. Am. Chem. Soc. 113, 2940 (1991).
Example 1
A methylene chloride/toluene solution (2/1 v/v) containing 0.025 g Cδo and 0.5 g (Bu4N)+l(PF6)_1 was electrolyzed at. -0.70 V vs. SCE for a time sufficient to reduce CδO- Electronic spectroscopy and ESR spectra indicated the formation of the alkyl ammonium Cδo fuller¬ ide salt, (Bu4N)+lC60_1- Cyclic voltommetry and DPP confirmed the presence of Ceo- .
Example 2
The procedure specified in Example 1 was employed using C70 and produced the alkylammonium C70*1 fulleride salt (Bu4N)+lC70"1, as shown by electrochemical and ESR analysis.
Example 3
A tetrahydrofuran solution containing 0.002 g Cδo and 0.30 g NaBF4 was electrolyzed at -0.7 V vs. SCE for a time sufficient to reduce the Ceo. The properties of the resulting inorganic fulleride salt Na+lCβO"1 are similar to those of its BU4N+C60"-*- counterpart in
Example 1 (as determined by electronic and magnetic resonance spec¬ troscopy).
Example 4
A polar solvent system consisting of a dimethyl sulfoxide DMSO/toluene solution (6/1 v/v) containing a suspension of 0.1 g Cδo and 0.25 KC1 was electrolyzed at -0.45 V vs. SCE for a time sufficient to produce C60~*- The solution turned red at the end of the reduc¬ tion. Addition of toluene (about 5:1 toluene/DMSO) and refrigeration overnight at -20°C allowed for the removal of most of DMSO and some toluene as a frozen solid. Addition of freshly distilled diethyl ether to the remaining solution resulted in the precipitation of KC60 as a black powder, which was isolated via filtration or decanting the liquid. Electronic and ESR spectra of DMSO solutions of the solid confirmed the presence of C60" in the inorganic K+Cδo"-- fulleride salt. Only traces of chloride ions were detected via scanning elec¬ tron microscopy energy dispersive spectroscopy, which also confirmed the presence of the KCδo salt.
Example 5
The procedure of Example 4 was repeated using KBr instead of KC1 to produce K+1C60"1 fulleride salt.
Example 6
This example illustrates the use of CβO as a solid state electrode component. A toluene solution of CδO w s deposited on a glassy carbon electrode. Upon solvent evaporation, the electrode was coated with solid Cδø. The coated electrode was immersed in an acetonitrile solution containing 0.4 g BU4NPF6 as the supporting electrolyte. Ceo and its anions are not soluble in acetonitrile. Cyclic voltametric scans revealed the reversible formation of Ceo"1- C60"-**, Cβθ" anions in the solid film. The additions of electrons to C60 was reversible; the CV scans are similar to those obtained previ¬ ously by using a solution of Cδo- A control CV analysis of a
suspension of C60 in acetonitrile solution containing the same sup¬ porting electrolyte revealed practically no fullerene-anion formation.
Claims (10)
1. A composition of matter having the formula AnCx wherein A is a monovalent cation, wherein Cx is a fullerene anion, selected from the group consisting of CβO and C70, and wherein n is an integer from 1 to 3.
2. The composition of claim 1 wherein the monovalent cation is selected from the group consisting of ammonium, alkyl ammonium, alkali metal cations, organophosphonium and organoarsoniu cations
3. The composition of claim 1 wherein the fullerene anion is selected from the group consisting of monovalent, divalent and trivalent anions.
4. A method for preparing a fulleride salt composition comprising:
applying an electrical potential to a non-aqueous solution of a fullerene selected from the group consisting of Cδo and C70 and a salt containing a monovalent cation, A, selected from the group con¬ sisting of ammonium, alkyl ammonium, alkali metal cations, organo¬ phosphonium and organoarsonium cations, for a time sufficient to prepare a composition having the formula AnCx wherein A is a mono¬ valent cation, and wherein n is an integer from 1 to 3, and wherein Cx is a fullerene anion selected from the group consisting of Cδo and C70-
5. The method of claim 4 wherein the non-aqueous solution is an organic solvent system.
6. The composition of claim 1 wherein An is selected from the group consisting of Na, K, BU4N and h4P, wherein Bu is butyl and wherein Ph is selected from the group consisting of phenyl and phenyl-substituted groups.
7. A method for selectively generating a soluble salt of fullerenes from a solution of fullerenes and hydrocarbons comprising: applying an electrical potential to said solution wherein the electri¬ cal potential is in a range equal to the potential sufficient to reduce the fullerene to the corresponding fullerene anions and wherein the electric potential is within the range of the chemical inertness of the hydrocarbons, for a time sufficient to generate said fullerene anions.
8. The method of claim 6 wherein the electrical potential is from about zero to about -0.7 V, and wherein the fullerene anion is selected from the group consisting of C60"1 when the fullerene is C60 and C70"*-* when the fullerene is C70.
9. The method of claim 7 wherein the electrical potential is from about -0.80 V to about -1.1 V, wherein the fullerene anion -- is selected from the group consisting of C60"-*- when the fullerene is C6Q and C70"2 when the fullerene is C70.
10. The method of claim 7 wherein the electrochemical potential is from about -1.3 V to about -1.7 V, and wherein the fullerene anion is selected from the group consisting of Cβo-3 when the fullerene is Ceo and C70"3 when the fullerene is C70.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79839091A | 1991-11-26 | 1991-11-26 | |
| US798390 | 1991-11-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU3223093A true AU3223093A (en) | 1993-06-28 |
Family
ID=25173281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU32230/93A Abandoned AU3223093A (en) | 1991-11-26 | 1992-11-23 | Novel salts of fullerenes |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0614444A4 (en) |
| JP (1) | JPH07501782A (en) |
| AU (1) | AU3223093A (en) |
| CA (1) | CA2124191A1 (en) |
| WO (1) | WO1993011067A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU685064B2 (en) * | 1992-09-16 | 1998-01-15 | Hoechst Aktiengesellschaft | Process for separating fullerenes |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5811460A (en) | 1994-01-24 | 1998-09-22 | The Regents Of The University Of California | Water soluble fullerenes with antiviral activity |
| ES2255933T3 (en) * | 2000-10-20 | 2006-07-16 | Prysmian Cavi E Sistemi Energia S.R.L. | PROCEDURE TO PRODUCE A METAL FULLERENUR. |
| EP2322475A1 (en) * | 2009-11-17 | 2011-05-18 | Siemens Aktiengesellschaft | Method of synthesis of a fulleride of metal nano-cluster and material comprising a fulleride of metal nano-cluster |
| CN109053468B (en) * | 2018-07-03 | 2020-12-15 | 苏州大学 | Fullerene ammonium tripropionate derivative, preparation method and application thereof |
-
1992
- 1992-11-23 WO PCT/US1992/010120 patent/WO1993011067A1/en not_active Application Discontinuation
- 1992-11-23 EP EP93900639A patent/EP0614444A4/en not_active Withdrawn
- 1992-11-23 CA CA002124191A patent/CA2124191A1/en not_active Abandoned
- 1992-11-23 AU AU32230/93A patent/AU3223093A/en not_active Abandoned
- 1992-11-23 JP JP5510208A patent/JPH07501782A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU685064B2 (en) * | 1992-09-16 | 1998-01-15 | Hoechst Aktiengesellschaft | Process for separating fullerenes |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2124191A1 (en) | 1993-06-10 |
| WO1993011067A1 (en) | 1993-06-10 |
| EP0614444A1 (en) | 1994-09-14 |
| JPH07501782A (en) | 1995-02-23 |
| EP0614444A4 (en) | 1995-03-15 |
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