Pentagon-Fused Hollow Fullerene in C<sub>78</sub> Family Retrieved by Chlorination

Tan, Yuan‐Zhi; Li, Jia; Zhou, Ting; Feng, Yu‐Qi; Lin, Shuichao; Lü, Xin; Zhan, Zhuang‐Ping; Xie, Su‐Yuan; Huang, Rong‐Bin; Zheng, Lan‐Sun

doi:10.1021/ja102887t

Cited by 33 publications

(31 citation statements)

References 47 publications

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“…However, non‐IPR fullerenes can be stabilized by endohedral encapsulation of metal clusters or by exohedral derivatization 12. 13 In particular, in situ chlorination during conventional fullerene synthesis was found to be efficacious in stabilizing non‐IPR fullerenes 14–23. Over the past ten years, several unconventional carbon cages were captured and separated by using this approach.…”

Section: Introductionmentioning

confidence: 99%

Capturing the Antiaromatic ^#6094C₆₈ Carbon Cage in the Radio‐Frequency Furnace

Amsharov

Ziegler

Mueller

et al. 2012

Chemistry A European J

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Although all fullerenes do not satisfy the classical aromaticity condition, as a result of their nonplanar nature, they experience effective stabilization due to extensive cyclic π-electron delocalization and exhibit pronounced "spherical aromaticity". This feature has raised the question of the opposite phenomenon, that is, the existence of antiaromatic carbon cages. Here the first experimental evidence of the existence of antiaromatic fullerenes is reported. The elusive (#6094)C(68) was effectively captured as C(68)Cl(8) by in situ chlorination in the gas phase during radio-frequency synthesis. The chlorinated cage was separated by means of multistage HPLC, and its connectivity unambiguously determined by single-crystal X-ray analysis. Halogen-stripped pristine (#6094)C(68) was monitored by mass spectrometry of the chlorinated C(68)Cl(8) cage. Quantum chemical calculations reveal the highly antiaromatic character of (#6094)C(68), in accordance with all geometric, energetic, and magnetic criteria of aromaticity. Chlorine addition leads to substantial stabilization of the cage owing to aromatization in the resulting C(68)Cl(8), which explains its high abundance in the primary fullerene soot. This work provides new insights into the process of fullerene formation and better understanding of aromaticity phenomena in general.

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Section: Introductionmentioning

confidence: 99%

Capturing the Antiaromatic ^#6094C₆₈ Carbon Cage in the Radio‐Frequency Furnace

Amsharov

Ziegler

Mueller

et al. 2012

Chemistry A European J

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“…The first small fullerene #271 C 50 (the Fowler-Manolopoulos nomenclature to differentiate isomers is specified by symmetry and/or by spiral algorithm) was trapped and stabilized by chlorine atoms as #271 C 50 Cl 10 in 2004 [271]. Since then the fullerene cage has been exohedrically functionalized by introducing hydrogen or chloride atoms on the cage surface, to produce a variety of non-IPR fullerene derivatives, such as C 64 H 4 [272], C 71 H 2 [273], C 78 Cl 8 [274], etc.…”

Section: Fullerenes For Molecular Wiresmentioning

confidence: 99%

Buckyballs

Delgado

Filippone

Giacalone

et al. 2013

Topics in Current Chemistry

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Buckyballs represent a new and fascinating molecular allotropic form of carbon that has received a lot of attention by the chemical community during the last two decades. The unabating interest on this singular family of highly strained carbon spheres has allowed the establishing of the fundamental chemical reactivity of these carbon cages and, therefore, a huge variety of fullerene derivatives involving [60] and [70]fullerenes, higher fullerenes, and endohedral fullerenes have been prepared. Much less is known, however, of the chemistry of the uncommon non-IPR fullerenes which currently represent a scientific curiosity and which could pave the way to a range of new fullerenes. In this review on buckyballs we have mainly focused on the most recent and novel covalent chemistry of fullerenes involving metal catalysis and asymmetric synthesis, as well as on some of the most significant advances in supramolecular chemistry, namely H-bonded fullerene assemblies and the search for efficient concave receptors for the convex surface of fullerenes. Furthermore, we have also described the recent advances in the macromolecular chemistry of fullerenes, that is, those polymer molecules endowed with fullerenes which have been classified according to their chemical structures. This review is completed with the study of endohedral fullerenes, a new family of fullerenes in which the carbon cage of the fullerene contains a metal, molecule, or metal complex in the inner cavity. The presence of these species affords new fullerenes with completely different properties and chemical reactivity, thus opening a new avenue in which a more precise control of the photophysical and redox properties of fullerenes is possible. The use of fullerenes for organic electronics, namely in photovoltaic applications and molecular wires, complements the study and highlights the interest in these carbon allotropes for realistic practical applications. We have pointed out the so-called non-IPR fullerenes - those that do not follow the isolated pentagon rule - as the most intriguing class of fullerenes which, up to now, have only shown the tip of the huge iceberg behind the examples reported in the literature. The number of possible non-IPR carbon cages is almost infinite and the near future will show us whether they will become a reality.

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“…Because it is known that fullerene species can undergo transformations during storage under sunlight irradiation, [41] it cannot be ruled out that C 60 C 14 Cl 8 results from reaction of perchlorinated pyracylene and C 60 since both are present in the raw soot extract. According to the structural data, C 14 Cl 8 is attached to C 60 at a [6,6] bond resulting in a four-membered ring of sp 3 carbon atoms.…”

Section: A C H T U N G T R E N N U N G [2+2]mentioning

confidence: 99%

Perchloropyracylene and its Fusion with C₆₀ by Chlorine‐Assisted Radio‐Frequency Furnace Synthesis

Mueller

Ziegler

Amsharov

et al. 2011

Chemistry A European J

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Elusive perchloropyracylene has been obtained during conventional fullerene synthesis in a chlorine-containing atmosphere by using the radio-frequency furnace technique. In contrast to its hydrocarbon analogue, the title compound was found to be unexpectedly stable. Although the high stability of perchloropyracylene impedes its direct addition to C(60) fullerene, the corresponding adduct was found in the synthesis products extracted from the raw soot. Both new species were separated and unambiguously characterized by single-crystal X-ray analysis. According to experimental observations and quantum chemical calculations, the addition of perchloropyracylene to the C(60) fullerene can only be realized by involving highly reactive species such as C(14) clusters displaying the pyracylene connectivity. Such a viable mechanism includes capturing of free or partially chlorinated C(14) clusters with pyracylene-type connectivity by the fullerene molecule and subsequent stabilization through chlorine addition. The data obtained provide experimental evidence for the presence of pyracylene-like C(14) clusters in the gas phase, which have evolved during the graphite vaporization process. According to the pentagon road mechanism, such clusters are regarded as crucial intermediates in fullerene formation.

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Pentagon-Fused Hollow Fullerene in C₇₈ Family Retrieved by Chlorination

Cited by 33 publications

References 47 publications

Capturing the Antiaromatic ^#6094C₆₈ Carbon Cage in the Radio‐Frequency Furnace

Capturing the Antiaromatic ^#6094C₆₈ Carbon Cage in the Radio‐Frequency Furnace

Buckyballs

Perchloropyracylene and its Fusion with C₆₀ by Chlorine‐Assisted Radio‐Frequency Furnace Synthesis

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Pentagon-Fused Hollow Fullerene in C78 Family Retrieved by Chlorination

Cited by 33 publications

References 47 publications

Capturing the Antiaromatic #6094C68 Carbon Cage in the Radio‐Frequency Furnace

Capturing the Antiaromatic #6094C68 Carbon Cage in the Radio‐Frequency Furnace

Buckyballs

Perchloropyracylene and its Fusion with C60 by Chlorine‐Assisted Radio‐Frequency Furnace Synthesis

Contact Info

Product

Resources

About

Pentagon-Fused Hollow Fullerene in C₇₈ Family Retrieved by Chlorination

Capturing the Antiaromatic ^#6094C₆₈ Carbon Cage in the Radio‐Frequency Furnace

Capturing the Antiaromatic ^#6094C₆₈ Carbon Cage in the Radio‐Frequency Furnace

Perchloropyracylene and its Fusion with C₆₀ by Chlorine‐Assisted Radio‐Frequency Furnace Synthesis