Issue 31, 2010

EPR spectrum of the Y@C82 metallofullerene isolated in solid argon matrix: hyperfine structure from EPR spectroscopy and relativistic DFT calculations

Abstract

The EPR spectrum of the Y@C82 molecules isolated in solid argon matrix was recorded for the first time at a temperature of 5 K. The isotropic hyperfine coupling constant (hfcc) Aiso = 0.12 ± 0.02 mT on the nucleus 89Y as derived from the EPR spectrum is found in more than two times greater than that obtained in previous EPR measurements in liquid solutions. Comparison of the measured hfcc on a metal atom with that predicted by density-functional theory calculations (PBE/L22) indicate that relativistic method provides good agreement between experiment in solid argon and theory. Analysis of the DFT calculated dipole–dipole hf-interaction tensor and electron spin distribution in the endometallofullerenes with encaged group 3 metal atoms Sc, Y and La has been performed. It shows that spin density on the scandium atom represents the Sc dyz orbital lying in the symmetry plane of the C2v fullerene isomer and interacting with two carbon atoms located in the para-position on the fullerene hexagon. In contrast, the configuration of electron spin density on the heavier atoms, Y and La, is associated with the hybridized orbital formed by interaction of the metal dyz and py electronic orbitals.

Graphical abstract: EPR spectrum of the Y@C82 metallofullerene isolated in solid argon matrix: hyperfine structure from EPR spectroscopy and relativistic DFT calculations

Supplementary files

Article information

Article type
Paper
Submitted
14 Dec 2009
Accepted
22 Apr 2010
First published
09 Jun 2010

Phys. Chem. Chem. Phys., 2010,12, 8863-8869

EPR spectrum of the Y@C82 metallofullerene isolated in solid argon matrix: hyperfine structure from EPR spectroscopy and relativistic DFT calculations

E. Ya. Misochko, A. V. Akimov, V. A. Belov, D. A. Tyurin, V. P. Bubnov, I. E. Kareev and E. B. Yagubskii, Phys. Chem. Chem. Phys., 2010, 12, 8863 DOI: 10.1039/B926279B

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