Selective Extraction of Endohedral Metallofullerenes Using a Mixed Solvent of Triethylamine and Acetone

Kodama, Tohru; Higashi, Korenari; Ichikawa, Takafumi; Suzuki, Satoshi; Nishikawa, Hiroyuki; Ikemoto, Isao; Kikuchi, Kôichi; Achiba, Yohji

doi:10.1246/cl.2005.464

Cited by 10 publications

(8 citation statements)

References 5 publications

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“…We obtained the anion Y 2 @C 80 − through chemical reduction of the arc discharge produced soot by using trimethylamine as the reduction agent. 41 The reduced product contains anions Y 2 @C 80 − and Y@C 82 − (Figure 4d). The diamagnetic anion Y@C 82 − does not have a major influence on the ESR measurements on Y 2 @C 80 − .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Then, Y 2 @C 80 and Y@C 82 were selectively reduced and extracted from the raw soot. Trimethylamine (TEA) is a substantially strong electron donor and is able to reduce metallofullerenes to their anions or form donor–acceptor complex with metallofullerenes . In addition, the solvent polarity has significant influence on the reduction potential of metallofullerenes .…”

Section: Methodsmentioning

confidence: 99%

“…Trimethylamine (TEA) is a substantially strong electron donor and is able to reduce metallofullerenes to their anions or form donor−acceptor complex with metallofullerenes. 41 In addition, the solvent polarity has significant influence on the reduction potential of metallofullerenes. 42 In this study, 1 g of raw soot was reacted with 1 mL of TEA in a mixed solvent of 20 mL of acetone and 30 mL of toluene at the boiling temperature for 5 h under nitrogen atmosphere.…”

Section: ■ Introductionmentioning

confidence: 99%

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Endohedral Metallofullerene M₂@C₈₀: A New Class of Magnetic Superhalogen

Jiang

Zhang

et al. 2019

J. Phys. Chem. C

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Superhalogen is a special class of atomic clusters whose electron affinity is larger than that of chlorine atom, which has the largest electron affinity in the periodic table of elements. In this paper, we report the fabrication of a new class of magnetic superhalogen by encapsulating two rareearth metal atoms into the I h symmetrical C 80 fullerene. The as-produced metallofullerene has an electronic configuration of M 2 5+ @C 80 5− . The addition of an extra electron to the molecule leads to the formation of a highly stable structure M 2 5+ @C 80 6− . Density functional theory calculations reveal that M 2 @C 80 has a larger electron affinity than the chlorine atom. Thus, M 2 @C 80 can be classified as superhalogen. The magnetic properties of the M 2 @C 80 superhalogens are associated with the single-electron metal−metal molecular orbital and the partially filled f electron shell of the metal atoms. Electron spin resonance measurement discloses the paramagnetic character of Y 2 @C 80 − and the strong coupling effect between the unpaired electron and the Y nuclei. The outer fullerene cage provides a suitable environment for protecting the unconventional valence and spin states of the inner metal atoms. A variety of superhalogens with distinct magnetic properties can be obtained by encapsulating different lanthanide metal atoms into the C 80 fullerene. Such superhalogens can serve as building blocks of materials with tailored magnetic properties.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Endohedral Metallofullerene M₂@C₈₀: A New Class of Magnetic Superhalogen

Jiang

Zhang

et al. 2019

J. Phys. Chem. C

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“…Their work provides a simple method for selective extraction of M 2 @C 80 metallofullerene. Kodama and coworkers reported that Ce-metallofullerenes (Ce@C 82 , Ce 2 @C 78 , Ce 2 @C 80 ) can be extracted selectively using a mixed solvent of triethylamine and acetone [ 61 ]. They proposed that the reduction of Ce-metallofullerenes by triethylamine or the formation of metallofullerene-triethylamine donor-accepter complexes is responsible for the selective extraction of metallofullerenes.…”

Section: Separation/purification Of Metallofullerenes Through Chemmentioning

confidence: 99%

Non-Chromatographic Purification of Endohedral Metallofullerenes

2017

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The purification of endohedral metallofullerenes by high performance liquid chromatography is very time-consuming and expensive. A number of rapid and inexpensive non-chromatographic methods have thus been developed for large-scale purification of metallofullerenes. In this review, we summarize recent advances in non-chromatographic purification methods of metallofullerenes. Lewis acid-based complexation is one of the most efficient and powerful methods for separation of metallofullerenes from empty fullerenes. The first oxidation potential of metallofullerenes is a critical factor that affects the separation efficiency of the Lewis acid-based method. Supramolecular methods are effective for separation of fullerenes and metallofullerenes that are different in size and shape. Chemical/electrochemical reduction and exohedral functionalization are also utilized to separate and purify metallofullerenes on a large scale.

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“…Non-HPLC approaches for endohedral separations take advantage of differences between metallofullerenes and empty-cage fullerenes, which lack an electron transfer from the cluster to the cage surface due to the absence of an encapsulated metal(s). Features of emptycages and metallofullerenes that can be manipulated include differences in their physical properties, 5,6 chemical reactivity, [7][8][9][10][11][12][13][14][15][16] and electrochemical/redox [17][18][19][20][21][22][23] behaviour.…”

Section: Introductionmentioning

confidence: 99%

Fractionation of rare-earth metallofullerenes via reversible uptake and release from reactive silica

2014

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Minimal research exists for non-chromatographic separations of rare-earth metallofullerenes containing di-metallic (M2), di-metallic carbide (M2C2), and tri-metallic nitride (M3N) clusters trapped inside fullerene cages. Herein, we demonstrate a non-HPLC method (i.e., SAFA, Stir and Filter Approach) for purifying Er3N@Ih-C80, a rare-earth, metallic nitride clusterfullerene. We describe a strategic method that chemically releases rare-earth metallofullerenes (e.g., M2@C2n, M3N@C2n) trapped by aminosilica during SAFA. Recovery of metallofullerenes from spent silica represents a "green approach" because the spent silica and its useful, immobilized rare-earth metallofullerenes would have been discarded as waste material. We observe selectivity during metallofullerene uptake to aminosilica and also during its release from spent silica via addition of CS2. We describe a procedure to obtain samples enriched in M2 and M3N endohedrals. M2C2n fractions from our SAFA release process contain a wide range of higher metallofullerenes (e.g., Gd2C90-Gd2C140 or Er2C76-Er2C122). It is facile to obtain samples enriched in M3N@C82-M3N@C92. Note that unreacted M3N@C80 remains in the filtrate. The strategy for handling rare-earth metallofullerenes with different degrees of reactivity toward aminosilica is also discussed.

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Selective Extraction of Endohedral Metallofullerenes Using a Mixed Solvent of Triethylamine and Acetone

Cited by 10 publications

References 5 publications

Endohedral Metallofullerene M₂@C₈₀: A New Class of Magnetic Superhalogen

Endohedral Metallofullerene M₂@C₈₀: A New Class of Magnetic Superhalogen

Non-Chromatographic Purification of Endohedral Metallofullerenes

Fractionation of rare-earth metallofullerenes via reversible uptake and release from reactive silica

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Selective Extraction of Endohedral Metallofullerenes Using a Mixed Solvent of Triethylamine and Acetone

Cited by 10 publications

References 5 publications

Endohedral Metallofullerene M2@C80: A New Class of Magnetic Superhalogen

Endohedral Metallofullerene M2@C80: A New Class of Magnetic Superhalogen

Non-Chromatographic Purification of Endohedral Metallofullerenes

Fractionation of rare-earth metallofullerenes via reversible uptake and release from reactive silica

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Product

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Endohedral Metallofullerene M₂@C₈₀: A New Class of Magnetic Superhalogen

Endohedral Metallofullerene M₂@C₈₀: A New Class of Magnetic Superhalogen