Deviation from the planarity--a large Dy3N cluster encapsulated in an Ih-C80 cage: an X-ray crystallographic and vibrational spectroscopic study

J Am Chem Soc. 2006 Dec 27;128(51):16733-9. doi: 10.1021/ja066814i.

Abstract

The high-yield synthesis of Dy3N@C80 (I) opens the possibility of characterizing its molecular and vibrational structures. We report on the structure determination of Dy3N@C80 (I) by X-ray crystallographic study of single crystal of Dy3N@C80.Ni(OEP).2C6H6, revealing a nearly planar Dy3N cluster encapsulated in an Ih-C80 cage. The vibrational structure of Dy3N@C80 (I) is studied by Fourier transform infrared (FTIR) and Raman spectroscopy in combination with force-field calculations. A correlation was found between the antisymmetric metal-nitrogen stretching vibration and the structure of the M3N cluster of M3N@C80 (I) (M = Y, Gd, Tb, Dy, Ho, Er, Tm). Moreover, a stronger interaction between the encaged nitride cluster and the C80 carbon cage was found in the class II M3N@C80 (I) (M = Y, Gd, Tb, Dy, Ho, Er, Tm) than in Sc3N@C80 (I). This study demonstrates that the cluster size plays the dominating role in the structure of the M3N cluster in M3N@C80 (I).

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Crystallography, X-Ray
  • Dysprosium / chemistry*
  • Fullerenes / chemistry*
  • Models, Molecular
  • Nickel / chemistry
  • Organometallic Compounds / chemical synthesis
  • Organometallic Compounds / chemistry*
  • Sensitivity and Specificity
  • Spectroscopy, Fourier Transform Infrared / methods
  • Spectrum Analysis, Raman / methods*
  • Time Factors
  • Vibration

Substances

  • Fullerenes
  • Organometallic Compounds
  • Dysprosium
  • Nickel