Issue 10, 2013
From the journal:

Physical Chemistry Chemical Physics

Application of MCD spectroscopy and TD-DFT to endohedral metallofullerenes for characterization of their electronic transitions†

Michio Yamada,a   Zdenek Slanina,b   Naomi Mizorogi,b   Atsuya Muranaka,c   Yutaka Maeda,a   Shigeru Nagase,*d   Takeshi Akasaka*b  and  Nagao Kobayashi*e  

* Corresponding authors

a Department of Chemistry, Tokyo Gakugei University, Koganei, Japan
E-mail: myamada@u-gakugei.ac.jp
Fax: +81 42 329 7493
Tel: +81 42 329 7493

b Life Science Center of Tsukuba Advanced Research Alliance, University of Tsukuba, Tsukuba, Ibaraki 305-8577, Japan
E-mail: akasaka@tara.tsukuba.ac.jp
Fax: +81 29 853 6409
Tel: +81 29 853 6409

c Advanced Elements Chemistry Laboratory, Advanced Science Institute, RIKEN, Wako, Saitama 351-0198, Japan

d Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan

e Department of Chemistry, Graduate School of Science, Tohoku University, Sendai, Miyagi 980-8578, Japan

Abstract

We describe, for the first time, the application of magnetic circular dichroism (MCD) spectroscopy and time-dependent density functional theory (TD-DFT) calculations using B3LYP and M06-2X functionals to characterize the electronic transitions of endohedral metallofullerenes (EMFs). Results revealed that the electronic transitions of La@C2v–C82, La2@Ih–C80, and Sc3N@Ih–C80 can be assigned using these techniques. Particularly, a difference in the electronic transitions between La2@Ih–C80 and Sc3N@Ih–C80, which is invisible in absorption spectra, was observed clearly in MCD spectra. The observed MCD bands agree well with the oscillator strengths calculated using the B3LYP functional. In addition, the MCD bands of La2@Ih–C80 were altered upon [5,6]-addition, demonstrating that the MCD spectroscopy is sensitive to chemical functionalization of EMFs, and that it is therefore powerful to distinguish [5,6]-adducts from pristine La2@Ih–C80, although no marked difference exists in their absorption spectra.

Graphical abstract: Application of MCD spectroscopy and TD-DFT to endohedral metallofullerenes for characterization of their electronic transitions

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Article information

DOI
https://doi.org/10.1039/C3CP44096F
Article type
Paper
Submitted
18 Nov 2012
Accepted
17 Jan 2013
First published
17 Jan 2013

Phys. Chem. Chem. Phys., 2013,15, 3593-3601

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Application of MCD spectroscopy and TD-DFT to endohedral metallofullerenes for characterization of their electronic transitions

M. Yamada, Z. Slanina, N. Mizorogi, A. Muranaka, Y. Maeda, S. Nagase, T. Akasaka and N. Kobayashi, Phys. Chem. Chem. Phys., 2013, 15, 3593 DOI: 10.1039/C3CP44096F

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