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Chapter 11

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Arenes and Aromaticity

Carbon Clusters, Fullerenes, and Nanotubes

In general, the term nanoscale applies to dimensions on the
order of 1100 nanometers (1 nm 109 m), and one goal of
nanotechnology is to develop useful nanoscale devices (nanodevices). Because typical covalent bonds range from 0.10.2 nm,
chemical structures hold promise as candidates on which to
base nanodevices. Among them, much recent attention has
been given to carbon-containing materials and even elemental
carbon itself.
Until 1985, chemists recognized two elementary forms
(allotropes) of carbon: diamond and graphite. Then, Professors Harold W. Kroto (University of Sussex), Robert F. Curl,
and Richard E. Smalley (both of Rice University) reported that
laser-induced evaporation of graphite gave a species with a
molecular formula of C60 and proposed the spherical cluster
of carbon atoms now called buckminsterfullerene (Figure 11.5)
for it. Other closed carbon clusters, some larger than C60 and
some smaller, were also formed in the experiment. These forms
of carbon are now known as fullerenes, and Kroto, Smalley,
and Curl were awarded the 1996 Nobel Prize in Chemistry for
discovering them.

Figure 11.5
Buckminsterfullerene (C60). All of the carbon atoms are equivalent
and are sp2 -hybridized; each one simultaneously belongs to one fivemembered ring and two benzene-like six-membered rings.

Figure 11.6
A single-walled carbon nanotube (SWCNT). SWCNTs can be regarded
as a two-dimensional graphite sheet rolled into a cylinder. Credit: The
single-walled carbon nanotube in Figure 11.6 is from the Spartan model
provided by Dr. Warren J. Hehre of Wavefunction, Inc.

Research on fullerenes carried out at NEC Corporation

(Japan) and at IBM (United States) led in 1991 to the isolation
of fibrous clusters of single-walled carbon nanotubes (SWCNTs)
(Figure 11.6). SWCNTs have since been joined by multiwalled
carbon nanotubes (MWCNTs) (Figure 11.7) as well as nanotubes
containing elements other than carbon.
CNTs themselves are of interest because of their electrical
and mechanical properties, and functionally modified ones are
being examined in applications ranging from medical diagnosis and therapy to photovoltaic systems. The methods used to
add functionality to a CNT include among others: (1) covalent
attachment of a reactive group to the CNT via a chemical reaction, and (2) noncovalent coating of the outer surface of the CNT
with a substance that itself bears a functional substituent.
Continued

inexpensive organic solvent because it has similar solvent properties but has not been
determined to be carcinogenic in the cell systems and at the dose levels that benzene is.

11.9 Reactions of Arenes: A Preview

Well examine the chemical properties of aromatic compounds from two different
perspectives:
1. One mode of chemical reactivity involves the ring itself as a functional group and
includes
(a) Reduction and oxidation
(b) Electrophilic aromatic substitution
Reduction of arenes by catalytic hydrogenation was described in Section 11.3. A different
method using Group 1 metals as reducing agents, which gives 1,4-cyclohexadiene derivatives, will be presented in Section 11.10. Oxidations of aromatic compounds are discussed in
Chapter 22. Electrophilic aromatic substitution is the most important reaction type exhibited by benzene and its derivatives and constitutes the entire subject matter of Chapter 12.