Preparation and crystallographic characterization of C60Cl24

Shustova, Natalia B.; Popov, Alexey A.; Sidorov, Lev N.; Turnbull, A.P.; Kemnitz, Erhard; Troyanov, Sergey I.

doi:10.1039/b416341a

Cited by 48 publications

(75 citation statements)

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“…[3,4] As far as chloro [60]fullerenes are concerned, the situation is paradoxical. Although chlorination was one of the first C 60 derivatizations reported in the literature, revealing the formation of C 60 Cl 6 [5] and putative C 60 Cl n compounds with up to 24 chlorine atoms s-bonded to the C 60 cage, [6,7] structurally-characterized compounds such as T h -C 60 Cl 24 , [8] C 1 -C 60 Cl 28 , [9] C 2 -C 60 Cl 30 , [9] and D 3d -C 60 Cl 30 [10] have only been reported in the past few months (the compound C 60 Cl 6 is believed to have the same structure as C s -C 60 Br 6 based on its 13 C NMR spectrum [5] ). Nevertheless, after nearly 15 years the compositional purity of C 60 Cl 6 , which has always been assumed to be high, [5,11,12] has never been satisfactorily demonstrated (i.e., none of the three previous reports of its synthesis properly established its purity [5,11,12] ).…”

Section: Introductionmentioning

confidence: 99%

“…Dozens of C 60 derivatives containing from 2 to 48 fluorine atoms and, in many cases, other substituents as well have been extensively studied. [1,2] In addition, bromination of C 60 yielded the three single-composition/singleisomer products C s -C 60 Br 6 , C 2v -C 60 Br 8 , and T h -C 60 Br 24 , all of which have been structurally characterized. [3,4] As far as chloro [60]fullerenes are concerned, the situation is paradoxical.…”

Section: Introductionmentioning

confidence: 99%

“…The spectrum matched the literature spectrum. [8] Infrared spectra of 99 % pure C 60 Cl 6 were recorded by using a Bruker Equinox 55 FTIR spectrometer operating at 1 cm À1 resolution. Samples were either pressed pellets of pure C 60 Cl 6 or pressed pellets of C 60 Cl 6 diluted with KBr.…”

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Seven‐Minute Synthesis of Pure C_s‐C₆₀Cl₆ from [60]Fullerene and Iodine Monochloride: First IR, Raman, and Mass Spectra of 99 mol % C₆₀Cl₆

Kuvychko

Streletskii

Popov

et al. 2005

Chemistry A European J

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Three previously reported procedures for the synthesis of pure C(s)-C60Cl6 from C60 and ICl dissolved in benzene or 1,2-dichlorobenzene were shown to actually yield complex mixtures of products that contain, at best, 54-80% C(s)-C60Cl6 based on HPLC integrated intensities. MALDI mass spectrometry was used for the first time to identify other components of the reaction mixtures. An improved synthetic procedure was developed for the synthesis of about 150 mg batches of chlorofullerenes containing 90% C(s)-C60Cl6 based on HPLC intensities. The optimum reaction time was decreased from several days to seven minutes. Small amounts of the product were purified by HPLC (toluene eluent) to 99% purity. The pure compound C(s)-C60Cl6 is stable for at least three months as a solvent-free powder at 25 degrees C. The Raman, far-IR, and MALDI mass spectra of pure C(s)-C60Cl6 are reported for the first time. The Raman and far-IR spectra, the first reported for any C60Cl(n) chlorofullerene, were used to carry out a vibrational analysis of C(s)-C60Cl6 at the DFT level of theory.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Seven‐Minute Synthesis of Pure C_s‐C₆₀Cl₆ from [60]Fullerene and Iodine Monochloride: First IR, Raman, and Mass Spectra of 99 mol % C₆₀Cl₆

Kuvychko

Streletskii

Popov

et al. 2005

Chemistry A European J

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“…(1) and calculated one for C 1 -C 70 Cl 16 (below) using force-field scaling factors found for the C 60 Cl 24 molecule. [2] Angewandte Chemie…”

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confidence: 99%

“…In addition to C 60 Cl 6 , which was obtained many years ago and investigated by 13 C NMR and IR spectroscopy, [1] four highly chlorinated [60]fullerenes, C 60 Cl 24 , [2] C 60 Cl 28 , [3] and two isomers of C 60 Cl 30 , [3,4] have been prepared and characterized by means of single-crystal X-ray crystallography and IR spectroscopy. The application of this method to the chlorination of C 70 produced a highly chlorinated fullerene, C 70 Cl 28 , which, according to the singlecrystal X-ray crystallographic study, comprised three isomers with similar structures.…”

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confidence: 99%

A [70]Fullerene Chloride, C₇₀Cl₁₆, Obtained by the Attempted Bromination of C₇₀ in TiCl₄

Troyanov

Popov

2005

Angew Chem Int Ed

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The use of liquid inorganic chlorides as chlorinating agents for fullerenes resulted recently in the synthesis of several new chlorofullerenes. In addition to C 60 Cl 6 , which was obtained many years ago and investigated by 13 C NMR and IR spectroscopy, [1] four highly chlorinated [60]fullerenes, C 60 Cl 24 , [2] C 60 Cl 28 , [3] and two isomers of C 60 Cl 30 , [3,4] have been prepared and characterized by means of single-crystal X-ray crystallography and IR spectroscopy. The application of this method to the chlorination of C 70 produced a highly chlorinated fullerene, C 70 Cl 28 , which, according to the singlecrystal X-ray crystallographic study, comprised three isomers with similar structures.[5] Earlier, C 70 Cl 10 was prepared by treating C 70 with ICl in benzene; its addition pattern has been deduced from 13 C NMR spectroscopic analysis, [6a] substitution reactions, [6b] and theoretical modeling studies.[6c] Thus, the chlorination of the fullerenes under mild conditions results in "lower" chlorides, whereas the use of strong chlorinating agents at elevated temperatures produces "higher" chlorides of both [60]-and [70]fullerenes. These results raise the question as to whether "missing" intermediate chlorides could be obtained by variation of the reactants and/or reaction conditions. Herein, we report the synthesis of such an intermediate chloride of [70]fullerene, C 70 Cl 16 , and its characterization by single-crystal X-ray crystallography, IR spectroscopy, and DFT calculations. Notably, the new fullerene chloride was obtained during an attempt to brominate C 70 in TiCl 4 . Typically, neat bromine (0.5 mL) was added to a solution of C 70 (30 mg) in TiCl 4 (2.0 mL) in a glass ampoule. The ampoule was evacuated on cooling and sealed. A yellow crystalline precipitate formed after heating the mixture at 60-80 8C for 1-2 days. Work-up consisted of distilling off the bromine and excess TiCl 4 into a second section of the sealed ampoule by cooling it with liquid nitrogen. Alternatively, the ampoule was opened and the mixture was poured into 15 % HCl. The yellow precipitate so formed was washed with dilute HCl and then water before removal by filtration and drying at 50 8C for

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Radical Chemistry on Fullerenes

Tzirakis

Orfanopoulos

2012

Encyclopedia of Radicals in Chemistry, Biology and Materials

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The aim of this article is to provide a concise review mainly on the practical synthetic applications and to a lesser extent on the fundamentals of fullerenes' radical chemistry. From a practical point of view, we demonstrate that the employment of radical reactions in fullerene chemistry has led to the synthesis of a variety of structurally diverse fullerene derivatives which would be otherwise inaccessible. In this context, the major types of neutral or ion radical additions to C 60 are reported. Such reactions include the addition of radicals of different chemical nature, including C‐, Si‐, O‐, S‐, P‐, and metal‐centered radicals, to C 60 or C 70 . From a fundamental perspective, we report on some of the basic characteristics of the radical reactions of fullerenes, such as the tendency of free radicals to add, multiply, and fast to C 60 and the tendency of the resulting RC 60 · to dimerize.

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Preparation and crystallographic characterization of C60Cl24

Abstract: C60Cl24 has been synthesized by the chlorination of C60 with VCl4 or C60Br24 with SbCl5; the X-ray single crystal structure of C60Cl24.2Br2 confirmed the molecular T(h) symmetry in good agreement with the IR data and theoretical calculations.

Cited by 48 publications

References 12 publications

Seven‐Minute Synthesis of Pure C_s‐C₆₀Cl₆ from [60]Fullerene and Iodine Monochloride: First IR, Raman, and Mass Spectra of 99 mol % C₆₀Cl₆

Seven‐Minute Synthesis of Pure C_s‐C₆₀Cl₆ from [60]Fullerene and Iodine Monochloride: First IR, Raman, and Mass Spectra of 99 mol % C₆₀Cl₆

A [70]Fullerene Chloride, C₇₀Cl₁₆, Obtained by the Attempted Bromination of C₇₀ in TiCl₄

Radical Chemistry on Fullerenes

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Preparation and crystallographic characterization of C60Cl24

Abstract: C60Cl24 has been synthesized by the chlorination of C60 with VCl4 or C60Br24 with SbCl5; the X-ray single crystal structure of C60Cl24.2Br2 confirmed the molecular T(h) symmetry in good agreement with the IR data and theoretical calculations.

Cited by 48 publications

References 12 publications

Seven‐Minute Synthesis of Pure Cs‐C60Cl6 from [60]Fullerene and Iodine Monochloride: First IR, Raman, and Mass Spectra of 99 mol % C60Cl6

Seven‐Minute Synthesis of Pure Cs‐C60Cl6 from [60]Fullerene and Iodine Monochloride: First IR, Raman, and Mass Spectra of 99 mol % C60Cl6

A [70]Fullerene Chloride, C70Cl16, Obtained by the Attempted Bromination of C70 in TiCl4

Radical Chemistry on Fullerenes

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Seven‐Minute Synthesis of Pure C_s‐C₆₀Cl₆ from [60]Fullerene and Iodine Monochloride: First IR, Raman, and Mass Spectra of 99 mol % C₆₀Cl₆

Seven‐Minute Synthesis of Pure C_s‐C₆₀Cl₆ from [60]Fullerene and Iodine Monochloride: First IR, Raman, and Mass Spectra of 99 mol % C₆₀Cl₆

A [70]Fullerene Chloride, C₇₀Cl₁₆, Obtained by the Attempted Bromination of C₇₀ in TiCl₄