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A Facile Route to the Non‐IPR Fullerene Sc 3 N@C 68 : Synthesis, Spectroscopic Characterization, and Density Functional Theory Computations (IPR=Isolated Pentagon Rule)
Author(s) -
Yang Shangfeng,
Kalbac Martin,
Popov Alexey,
Dunsch Lothar
Publication year - 2006
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200600261
Subject(s) - fullerene , molecular vibration , yield (engineering) , spectral line , cluster (spacecraft) , density functional theory , absorption spectroscopy , chemistry , spectroscopy , computational chemistry , materials science , molecule , physics , organic chemistry , optics , quantum mechanics , astronomy , computer science , metallurgy , programming language
Owing to the unique feature of the non‐IPR D 3 (isomer 6140) C 68 cage (IPR=isolated pentagon rule), Sc 3 N@C 68 has been attracting great interest in the fullerene community. Herein we report the first high‐yield synthesis of Sc 3 N@C 68 by the “reactive gas atmosphere” method and its facile isolation by single‐step HPLC to a high purity (≥99 %). Thus, Sc 3 N@C 68 is isolated in sufficient quantities for its further spectroscopic characterization, while the high purity of the sample ensures the reliability of the spectroscopic data obtained. In particular, the electronic and vibrational structures of Sc 3 N@C 68 were studied in detail experimentally and by theoretical computations. The assignment of the observed absorption bands to particular electronic transitions is given in detail on the basis of time‐dependent DFT computations. Vibrational spectroscopy of Sc 3 N@C 68 reveals good agreement between the measured spectra and the theoretically calculated spectra. A detailed assignment of the vibrational modes, including the Sc 3 N cluster modes, cage modes, and vibrations of the adjacent pentagons are discussed. This study reveals that the effect of Sc 3 N encapsulation in the cage is much more complicated than just a formal transfer of six electrons. Consequently the electronic and vibrational spectra of the carbon cage in Sc 3 N@C 68 cannot be adequately understood on the basis of a C 68 6− cage alone.