Prev. Article Next Article Table of Contents

Article

M₂@C₇₉N (M = Y, Tb): Isolation and Characterization of Stable Endohedral Metallofullerenes Exhibiting M−M Bonding Interactions inside Aza[80]fullerene Cages

Supporting Info

Tianming Zuo^‡, Liaosa Xu^‡, Christine M. Beavers^†, Marilyn M. Olmstead^†, Wujun Fu^‡, T. Daniel Crawford^‡, Alan L. Balch*^† and Harry C. Dorn*^‡

Departments of Chemistry, University of California, Davis, One Shields Avenue, Davis, California 95616, and Virginia Polytechnic Institute and State University, Blacksburg, Virginia 24061

J. Am. Chem. Soc., 2008, 130 (39), pp 12992–12997

DOI: 10.1021/ja802417d

Publication Date (Web): September 6, 2008

‡

Virginia Polytechnic Institute and State University.

†

University of California, Davis.

Abstract

Y₂@C₇₉N and Tb₂@C₇₉N have been prepared by conducting the Krtschmer−Huffman electric-arc process under 20 Torr of N₂ and 280 Torr of He with metal oxide-doped graphite rods. These new heterofullerenes were separated from the resulting mixture of empty cage fullerenes and endohedral fullerenes by chemical separation and a two-stage chromatographic process. Crystallographic data for Tb₂@C₇₉N·Ni(OEP)·2C₆H₆ demonstrate the presence of an 80-atom cage with idealized I_h symmetry and two, widely separated Tb atoms inside with a Tb−Tb separation of 3.9020(10) Å for the major terbium sites. The EPR spectrum of the odd-electron Y₂@C₇₉N indicates that the spin density largely resides on the two equivalent yttrium ions. Computational studies on Y₂@C₇₉N suggest that the nitrogen atom resides at a 665 ring junction in the equator on the fullerene cage and that the unpaired electron is localized in a bonding orbital between the two yttrium ions of this stable radical. Thus, the Tb−Tb bond length of the single-electron bond is an exceedingly long metal−metal bond.

View: Full Text HTML | Hi-Res PDF | PDF w/ Links

Tools

SciFinder Links

History

Published In Issue October 01, 2008
Article ASAPSeptember 06, 2008
Received: April 2, 2008

Recommend & Share

Related Content

Detection of a Family of Gadolinium-Containing Endohedral Fullerenes and the Isolation and Crystallographic Characterization of One Member as a Metal−Carbide Encapsulated inside a Large Fullerene CageJournal of the American Chemical Society
- Detection of a Family of Gadolinium-Containing Endohedral Fullerenes and the Isolation and Crystallographic Characterization of One Member as a Metal−Carbide Encapsulated inside a Large Fullerene Cage
  Hua Yang, Chunxin Lu, Ziyang Liu, Hongxiao Jin, Yuliang Che, Marilyn M. Olmstead and Alan L. Balch
  Journal of the American Chemical Society 2008 130 (51), pp 17296–17300
  Abstract: A series of di-gadolinium endohedrals that extends from Gd₂C₉₀ to Gd₂C₁₂₄ has been detected by mass spectrometry of the o-dichlorobenzene extract of the carbon soot produced by direct current arcing of graphite rods filled with a mixture of Gd₂O₃ and ...
  Abstract | Full Text HTML | PDF w/ Links | Hi-Res PDF
Syntheses and Structures of Phenyl-C₈₁-Butyric Acid Methyl Esters (PCBMs) from M₃N@C₈₀Organic Letters
- Syntheses and Structures of Phenyl-C₈₁-Butyric Acid Methyl Esters (PCBMs) from M₃N@C₈₀
  Chunying Shu, Wei Xu, Carla Slebodnick, Hunter Champion, Wujun Fu, Jonathan E. Reid, Hugo Azurmendi, Chunru Wang, Kim Harich, Harry C. Dorn and Harry W. Gibson
  Organic Letters 2009 11 (8), pp 1753–1756
  Abstract: Two new 6,6-open phenyl-C₈₁-butyric acid methyl ester metallofulleroids, M₃N@C₈₀PCBM (M = Sc, Y), were synthesized by diazoalkane addition reactions and fully characterized. The results demonstrate that the reactive sites are the same for M₃N@C₈₀ (M = ...
  Abstract | Full Text HTML | PDF w/ Links | Hi-Res PDF
Photoswitching in Azafullerene Encapsulated Single-Walled Carbon Nanotube FET DevicesJournal of the American Chemical Society
- Photoswitching in Azafullerene Encapsulated Single-Walled Carbon Nanotube FET Devices
  Yongfeng Li, Toshiro Kaneko, Jing Kong and Rikizo Hatakeyama
  Journal of the American Chemical Society 2009 131 (10), pp 3412–3413
  Abstract: The photoinduced electrical transport properties of C₅₉N@SWNTs are investigated by assembling them into FET devices. Our findings demonstrate that azafullerene molecules inside SWNTs make nanotube FET devices very sensitive to UV light exposure by the ...
  Abstract | Full Text HTML | PDF w/ Links | Hi-Res PDF

Article

M₂@C₇₉N (M = Y, Tb): Isolation and Characterization of Stable Endohedral Metallofullerenes Exhibiting M−M Bonding Interactions inside Aza[80]fullerene Cages