Structural Study of Three Isomers of Tm@C<sub>82</sub> by <sup>13</sup>C NMR Spectroscopy

Kodama, Tohru; Ozawa, Norio; Miyake, Yoko; Sakaguchi, Kôichi; Nishikawa, Hiroyuki; Ikemoto, Isao; Kikuchi, Kôichi; Achiba, Yohji

doi:10.1021/ja005839t

Cited by 60 publications

(66 citation statements)

References 12 publications

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“…Similar effects were observed in numerous 13 C NMR studies on Ce‐based mono‐ and dimetallofullerenes and their derivatives 23. To our knowledge, the only paramagnetic 13 C NMR studies of non‐Ce lanthanide metallofullerenes were reported for three isomers of Tm@C 82 24 and for the Pr@C 82 − anion 25. The influence of multiple 4f electrons on the carbon cage is still an unresolved question which requires further study.…”

Section: Resultsmentioning

confidence: 97%

Synthesis, Isolation, and Spectroscopic Characterization of Holmium‐Based Mixed‐Metal Nitride Clusterfullerenes: Ho_xSc_3−xN@C₈₀ (x=1, 2)

Zhang

Popov

Schiemenz

et al. 2012

Chemistry A European J

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The synthesis, isolation and spectroscopic characterization of holmium-based mixed metal nitride clusterfullerenes Ho(x) Sc(3-x) N@C(80) (x=1, 2) are reported. Two isomers of Ho(x) Sc(3-x) N@C(80) (x=1, 2) were synthesized by the reactive gas atmosphere method and isolated by multistep recycling HPLC. The isomeric structures of Ho(x) Sc(3-x) N@C(80) (x=1, 2) were characterized by laser-desorption time-of-flight (LD-TOF) mass spectrometry and UV/Vis/NIR, FTIR and Raman spectroscopy. A comparative study of M(x) Sc(3-x) N@C(80) (M=Gd, Dy, Lu, Ho) demonstrates the dependence of their electronic and vibrational properties on the encaged metal. Despite the distinct perturbation induced by 4f(10) electrons, we report the first paramagnetic (13) C NMR study on Ho(x) Sc(3-x) N@C(80) (I; x=1, 2) and confirm I(h) -symmetric cage structure. A (45) Sc NMR study on HoSc(2) N@C(80) (I, II) revealed a temperature-dependent chemical shift in the temperature range of 268-308 K.

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Section: Resultsmentioning

confidence: 97%

Synthesis, Isolation, and Spectroscopic Characterization of Holmium‐Based Mixed‐Metal Nitride Clusterfullerenes: Ho_xSc_3−xN@C₈₀ (x=1, 2)

Zhang

Popov

Schiemenz

et al. 2012

Chemistry A European J

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“…Compounds containing Tm 2+ are now known for organometallic complexes36,37,38 and also for endohedral fullerenes 39. As an example of the latter, the three isomers of Tm@C 82 have been formulated with the electronic distribution, Tm 2+ [C 82 ] 2− 40,41. For Tm@ C 3v -C 94, the use of the same C 3v -C 94 cage structure as found for the calcium compound suggests that the Tm 2+ [C 94 ] 2− electronic distribution is probable.…”

Section: Discussionmentioning

confidence: 99%

Isolation and Structural Characterization of Two Very Large, and Largely Empty, Endohedral Fullerenes: Tm@C_3v-C₉₄ and Ca@C_3v-C₉₄

et al. 2009

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The structures of two newly synthesized endohedral fullerenes -Tm@C 3v -C 94 and Ca@C 3v -C 94 -have been determined by single crystal X-ray diffraction on samples co-crystallized with Ni II (octaethylporphyrin). Both compounds exhibit the same cage geometry and conform to the isolated pentagon rule (IPR). The metal ions within these rather large cages are localized near one end and along the C 3 axis. While the calcium ion is situated over a C-C bond at a 6:6 ring junction, the thulium ion is positioned above a six-membered ring of the fullerene.

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“…The molecular symmetries of Tm@C 82 (B, A, C) were determined as C s , C 2 , and C 2v , respectively, by using NMR spectroscopy. [16] Therefore, one can deduce that the symmetries of Yb@C 82 (I, II, III) should be C s , C 2 , and C 2v , respectively. In our earlier report, the UV/Vis/near-IR absorption spectra of Yb@C 82 (I, II, III) were given, which were very similar to those of Tm@C 82 (B, A, C).…”

Section: Introductionmentioning

confidence: 98%

Electrochemical Survey: The Effect of the Cage Size and Structure on the Electronic Structures of a Series of Ytterbium Metallofullerenes

Shi

et al. 2005

Chemistry A European J

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The electrochemical properties of a series of metallofullerenes with different cages, namely, Yb@C74(II), Yb@C76(I, II), Yb@C78, Yb@C80, Yb@C82(I, II, III), and Yb@C84(II, III, IV), have been systematically investigated by cyclic and differential pulse voltammetry experiments for the first time. This article discusses the electronic structures of these metallofullerenes based on the results from these experiments. From previous electrochemical work and the above discussion, it is concluded that the nondegenerate LUMO is a common characteristic of the electronic structures of the higher fullerenes and monometallofullerenes. In addition, the effect of the cage on the electronic structure and properties of the metallofullerene is estimated from the plot of the reduction potential versus the carbon number of the metallofullerene. This estimation shows that usually the electronic structure and properties of the metallofullerene vary with cage size and structure. The cage structure is of particular importance for determining the electronic structure and properties. Moreover, an explanation concerning the abundance and stability of C82-based trivalent monometallofullerenes is given from an electronic structural standpoint.

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Structural Study of Three Isomers of Tm@C₈₂ by ¹³C NMR Spectroscopy

Cited by 60 publications

References 12 publications

Synthesis, Isolation, and Spectroscopic Characterization of Holmium‐Based Mixed‐Metal Nitride Clusterfullerenes: Ho_xSc_3−xN@C₈₀ (x=1, 2)

Synthesis, Isolation, and Spectroscopic Characterization of Holmium‐Based Mixed‐Metal Nitride Clusterfullerenes: Ho_xSc_3−xN@C₈₀ (x=1, 2)

Isolation and Structural Characterization of Two Very Large, and Largely Empty, Endohedral Fullerenes: Tm@C_3v-C₉₄ and Ca@C_3v-C₉₄

Electrochemical Survey: The Effect of the Cage Size and Structure on the Electronic Structures of a Series of Ytterbium Metallofullerenes

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Structural Study of Three Isomers of Tm@C82 by 13C NMR Spectroscopy

Cited by 60 publications

References 12 publications

Synthesis, Isolation, and Spectroscopic Characterization of Holmium‐Based Mixed‐Metal Nitride Clusterfullerenes: HoxSc3−xN@C80 (x=1, 2)

Synthesis, Isolation, and Spectroscopic Characterization of Holmium‐Based Mixed‐Metal Nitride Clusterfullerenes: HoxSc3−xN@C80 (x=1, 2)

Isolation and Structural Characterization of Two Very Large, and Largely Empty, Endohedral Fullerenes: Tm@C3v-C94 and Ca@C3v-C94

Electrochemical Survey: The Effect of the Cage Size and Structure on the Electronic Structures of a Series of Ytterbium Metallofullerenes

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Structural Study of Three Isomers of Tm@C₈₂ by ¹³C NMR Spectroscopy

Synthesis, Isolation, and Spectroscopic Characterization of Holmium‐Based Mixed‐Metal Nitride Clusterfullerenes: Ho_xSc_3−xN@C₈₀ (x=1, 2)

Synthesis, Isolation, and Spectroscopic Characterization of Holmium‐Based Mixed‐Metal Nitride Clusterfullerenes: Ho_xSc_3−xN@C₈₀ (x=1, 2)

Isolation and Structural Characterization of Two Very Large, and Largely Empty, Endohedral Fullerenes: Tm@C_3v-C₉₄ and Ca@C_3v-C₉₄