2608 Chem. Mater. 2010, 22, 2608–2615
DOI:10.1021/cm903870v
Direct Arc-Discharge Assisted Synthesis of C60H2(C3H5N):
A cis-1-Pyrrolino C60 Fullerene Hydride with Unusual Redox Properties
Ning Chen,† Sabrina Klod,† Peter Rapta,‡ Alexey A. Popov,† and Lothar Dunsch*,†
†Group of Electrochemistry and Conducting Polymers, Leibniz-Institute for Solid State and Materials
Research (IFW) Dresden, D-01171 Dresden, Germany, and Department of Physical Chemistry, Faculty of
Chemical and Food Technology, Slovak University of Technology, SK-81237 Bratislava, Slovak Republic
‡
Received December 29, 2009. Revised Manuscript Received February 23, 2010
€
By direct arc synthesis of C60H2(C3H5N) using a modified Kratschmer-Huffman method, it is
demonstrated for the first time that exohedral fullerenes with large side groups can be formed under
the arc and reactive gas atmosphere conditions. The thus formed novel pyrrolino fullerene hydride
was comprehensively characterized by UV-vis, infrared (IR), Raman and nuclear magnetic
resonance (NMR) and studied by means of electrochemistry and in situ electron spin resonance/
visible-near infrared (ESR/Vis-NIR) spectroelectrochemistry. The detailed NMR and absorption
spectroscopic studies show C60H2(C3H5N) as the fullerene hydride with a pyrrolino ring attached on
the vicinal position of two hydrogen atoms. This first cycloaddition adduct of C60H2 gives rise to an
unusual reversible dimerization of its anion radicals and a loss of cage hydrogen atoms at the third
electron transfer. The spectroelectrochemical study confirms the formation of a [C60H2(C3H5N)]-
radical and the diamagnetic state of [C60H2(C3H5N)] 2-. This study reveals a unique function of a
carbide structure like Al4C3 and the presence of a reactive gas atmosphere with NH3 in the formation
of such an exohedral pyrrolino structure C60H2(C3H5N).
Introduction
synthesis of trimetallic nitride fullerenes, nitrogen, ammo-
nia, and some other nitrogen containing chemicals like
Ca(CN)2 wereutilizedasthesourceofnitrogenatoms.12-20
Through the use of methane in the reactive gas atmosphere
method, the formation of new fullerene cages like C64H4
was demonstrated.21 The arc discharge applying a reactive
gas was extended to non-isolated pentagon rule (IPR)
structures like C50 and two Ih-symmetry-breaking C60
isomers using chlorine as a reactive gas to the burning
process.22,23
Various synthesis methods have been developed for the
preparative access to spherical cage carbon molecules like
fullerenes constructed from 12 pentagons and a large
1
€
number of hexagons. Among them, the Kratschmer-
Huffman method is most commonly used to prepare
empty cage and endohedral fullerenes.2,3 Fullerenes, in-
cluding endohedral fullerenes and unconventional full-
erenes, have been extensively grown in their number and
variety.4-11 Recently, a modified Kratschmer-Huffman
€
method, in which a reactive gas and chemicals are intro-
duced to the arc discharging process, was developed to
produce novel endohedral fullerene structures. In the
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*To whom correspondence should be addressed. E-mail: l.dunsch@
ifw-dresden.de.
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r
2010 American Chemical Society
pubs.acs.org/cm
Published on Web 03/10/2010